Search for an electron electric dipole moment with trappedmolecular ions
byHuanqian Loh
B.Sc., Massachusetts Institute of Technology, 2006

A thesis submitted to the
Faculty of the Graduate School of the
University of Colorado in partial fulfillmentof the requirements for the degree ofDoctor of Philosophy
Department of Physics
2013This thesis entitled:
Search for an electron electric dipole moment with trapped molecular ionswritten by Huanqian Loh
has been approved for the Department of Physics

Eric Cornell

Jun YeDate

The final copy of this thesis has been examined by the signatories, and we find that both thecontent and the form meet acceptable presentation standards of scholarly work in the above
mentioned discipline.

iii
Loh, Huanqian (Ph.D., Physics)
Search for an electron electric dipole moment with trapped molecular ions
Thesis directed by Prof. Eric Cornell

The search for a permanent electron electric dipole moment (eEDM) serves as a test offundamental symmetry violations and of physics beyond the Standard Model. Trapped molecularions in the 3 ∆1 metastable electronic state are suitable candidates for an eEDM search due totheir large effective electric fields and long electron spin coherence times. This thesis presents thequantum state manipulation and coherent spectroscopy of trapped HfF+ molecular ions in rotating
bias fields for an eEDM search. The quantum state manipulation, which involves preparation ofa large fraction of molecular ions in a single desired quantum state as well as rotational-stateresolved detection, is complicated by the lack of HfF+ spectroscopic information prior to the startof this thesis. We performed state preparation by first state-selectively autoionizing neutral HfF
such that 35% of the HfF+ are formed in a single rovibrational level of the electronic groundstate 1 Σ+ , and then transferring those ions into the desired Stark levels of a single hyperfinerovibrational manifold of the 3 ∆1 state. Rotational-state-resolved detection is accomplished byboth laser-induced fluorescence and resonance-enhanced multi-photon photodissociation, where thelatter is preferred as the state detection method of choice because its efficiency is two orders ofmagnitude higher compared to fluorescence. With the quantum state manipulation techniquesdeveloped, we performed Ramsey spectroscopy of the trapped HfF+ ions in the presence of rotating
bias electric and magnetic fields, demonstrating electron spin coherence times as long as 150 ms.
Finally, we present a preliminary measurement of the eEDM at the |de | < 10−25 e cm level.

Dedication

To Wah Sing, Hui Sok, Zhi Heng, and Travis.

Acknowledgements

This thesis work could not have been completed without the help of many people, most ofwhom are at JILA. JILA houses a wonderful scientific community, which I am fortunate to be apart of for my graduate school.
Of the people at JILA, I would first like to thank my graduate school advisor, Eric Cornell.
From painting intuitive pictures to calling us out on software issues, Eric is a boundless source of
creative ideas, an effective problem-solver, and a gifted teacher. I will miss his motivational emails
explaining the merits of higher data-collection efficiency in terms of spending less time in the lab
and more time skiing. As a mentor, Eric also cares deeply about his students. I am immensely
grateful to his concern and advice on issues ranging from health to career.
Jun Ye has been a fantastic co-advisor, injecting a healthy amount of enthusiasm into theeEDM experiment. His wealth of technical expertise on all things lasers, experience with molecules,
and persistent demand for scientific rigor have contributed to my growth as a scientist.
From the conception of this experiment, John Bohn and his former student Ed Meyer haveprovided both extensive theory support and a lively dose of humor. Chris Greene and his former
student Jia Wang taught us about angular momentum in the autoionization of Rydberg molecules.
We have also had many fruitful collaborations with Bob Field from MIT, who shared with us thefiner points of diatomic molecular structure and with whom we co-authored several papers.
Through the regular Cornell-Jin group meetings, Debbie Jin has offered much physical insight
into our problems and has a knack for asking questions that keep our minds focused on the big
picture. I would also like to thank the rest of the Cornell-Jin group members for their friendship,

vi
their patience, and their magnanimity in lending us various kinds of equipment. Similarly, ourexperiment has also benefited from our interactions with the Ye group, the Lewandowski group,
the Thompson group, the Nesbitt group and the Lineberger group. Our access to so many groupsof expertise within a single building — be it securing the last-minute loan of a servo loop filter or
obtaining technical advice on pulsed Nd:YAG lasers — has been instrumental to our experimental
progress.
JILA’s collaborative environment goes beyond the interactions between the research groups.
The technical staff in the instrument shop, electronics shop and computing department have provided critical support for our experiment, for which I am very grateful. Special mention goes to
Todd Ascinar for machining our ion trap, to Hans Green and Blaine Horner for many creative
vacuum-compatible solutions, to Terry Brown and Carl Sauer for advice on all things electronics,
and to J. R. Raith for his computer wizardry. Pam Leland and Krista Beck also made sure that
we never had to worry about administrative issues.
Much of the work in this thesis was performed together with my fellow eEDM labmates,
whom I have had the pleasure to work with at one point or another. Russ Stutz showed me theropes on the eEDM experiment and left the experiment in excellent running condition when hegraduated. Kang-Kuen Ni was one of my first friends in Boulder and joined the eEDM effort as
our powerhouse postdoc in the last 14 months. She has always encouraged me to push myself togreater heights, be it making a run for an eEDM measurement before graduating or convincing me
to ski through glades. Matt Grau and I have spent many late nights taking data or bolting vacuum
chambers, and over the years I think I may have learned more from him than I have taught him.
Kevin Cossel’s expertise on cavities, molecular spectroscopy and baked treats have greatly benefited
our experiment from his involvement in the comb spectroscopy setup and more recently, the ion
trap setup. With Kevin and Matt taking over the experiment, I am sure many exciting results willsoon be forthcoming. I would also like to thank Tyler Yahn, Laura Sinclair, Dan Gresh, Herbert
Looser, Tyler Coffey, Trent Fridey and Yiqi Ni for their impactful contributions to the JILA eEDM
effort. Tyler Yahn was a very talented machinist and keen learner; Laura Sinclair led the initial

vii
effort to perform comb spectroscopy on HfF+ ; Dan Gresh has made a huge impact on the molecular
spectroscopy of both HfF+ and ThF+ ; Herbert Looser was both a very patient physics teacher andan avid Labview programmer; Tyler Coffey, Trent Fridey and Yiqi Ni are undergraduates who havebuilt all sorts of useful apparatus for the experiment.
My graduate school career was partly financed by A*STAR, for which I am grateful.
Prior to my time at JILA, Vladan Vuletić, James Thompson and Jon Simon have been
instrumental in stoking my love for atomic, molecular and optical physics. I thank them for theirhonest advice and kind words of encouragement from my undergraduate days through the end of
graduate school.
My parents have always been very supportive of my decisions, and I thank them for theirboundless love and their regular visits to Boulder. To my brother, thank you for being my rolemodel and for all the stimulating discussions we have had in life. I am excited to share this thesis
with you. To my sister in-law, thank you for your invaluable friendship and advice.
I have been extremely lucky to pick up a second family while in graduate school. I am
indebted to Johannah Nicholson and Jeff Nicholson for loving me like their own daughter. To Joe
Cohen and the rest of the Nicholson family, thank you for the memorable times we spent outsideof JILA.
It is hard to imagine the completion of this thesis without the love and support of my husband,
Travis Nicholson. His non-judgmental character, combined with his extensive technical experience,
has rendered him almost always the first person with whom I bounce ideas off. From lending an
extra hand to tighten vacuum bolts at midnight to taking me on a lovely hike through fields ofColorado wildflowers, Travis has been responsible for keeping me sane and happy through the many
ups and downs of graduate school. Travis is my inspiration in his dedication to physics and to his
loved ones, and I look forward to our many adventures in life together.

Contents

Chapter
1 Introduction1

1.1

Motivation for an electron electric dipole moment (eEDM) search . . . . . . . . . . .

1

1.2

Measuring the eEDM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3

1.2.1

Figure-of-merit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3

1.2.2

HfF+ molecular ions for an eEDM measurement . . . . . . . . . . . . . . . .

7

1.2.3

Challenges of using HfF+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

1.3

Overview of thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

2 REMPI spectroscopy of neutral HfF [51]

16

2.1

Experiment setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

2.2

HfF spectra in the range 30000–33000 cm−1 . . . . . . . . . . . . . . . . . . . . . . . 19

2.3

Lower states of observed transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.3.1

A tool for understanding vibronic bands . . . . . . . . . . . . . . . . . . . . . 24

2.4

Rotational line strengths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

2.5

Large isotope shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

2.6Intermediate states for OODR autoionization . . . . . . . . . . . . . . . . . . . . . . 31

2.7

Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

3 Autoionization for preparing HfF+ in a single rovibronic (1 Σ+ ) state [52]3.1

36

Experiment setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

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3.2

Autoionizing states of hafnium fluoride . . . . . . . . . . . . . . . . . . . . . . . . . . 42

3.3

Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

3.4

Rotational distributions and parity propensities in autoionization decay . . . . . . . 47

3.5

Preservation of orientation in autoionization decay . . . . . . . . . . . . . . . . . . . 49

3.6

Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

4 Ion traps
4.1

4.2

4.3

54

Linear Paul trap basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.1.1

A simple picture for the quadrupole trap

4.1.2

Pseudopotential

4.1.3

Mathieu equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

4.1.4

Multiple ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

4.1.5

Rotating field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

JILA eEDM ion trap version 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.2.1

Trap construction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

4.2.2

Trap driver electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

4.2.3

Experiment sequence for ion trapping . . . . . . . . . . . . . . . . . . . . . . 67

Trap loading and characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.3.1

Basic assumptions and terminology . . . . . . . . . . . . . . . . . . . . . . . . 68

4.3.2

Trap loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

4.3.3

Microchannel plate transfer matrices . . . . . . . . . . . . . . . . . . . . . . . 73

4.3.4

Trap characterization I: patch charges . . . . . . . . . . . . . . . . . . . . . . 75

4.3.5

Trap characterization II: anharmonicities . . . . . . . . . . . . . . . . . . . . 79

4.4

Rotating field characterization

4.5

Fluorescence. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

5 Spin readout techniques (I): fluorescence
5.1. . . . . . . . . . . . . . . . . . . . 54

85

Experiment setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

x
5.1.1

Fluorescence collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

5.1.2

Scattered light, the nemesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

5.2

LIF signal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

5.3

Estimates for cavity-enhanced detection . . . . . . . . . . . . . . . . . . . . . . . . . 92

6 Spin readout techniques (II): photodissociation
6.1

6.2

6.3

6.4

98

Basics of photodissociation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.1.1

Direct photodissociation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99

6.1.2

Predissociation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101

Practical challenges and considerations . . . . . . . . . . . . . . . . . . . . . . . . . . 103
6.2.1

HfF+ creation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103

6.2.2

Lasers, lasers and more lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . 104

6.2.3

Hf+ detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107

Photodissociation spectroscopy of HfF+ . . . . . . . . . . . . . . . . . . . . . . . . . 110
6.3.1

An initial disappointment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110

6.3.2

HfF+ lines galore! . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

6.3.3

Nature of photodissociating state at 72000 cm−1 . . . . . . . . . . . . . . . . 114

Photodissociation as a readout tool . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
6.4.1

Saturation of dissociation transition . . . . . . . . . . . . . . . . . . . . . . . 116

6.4.2

Efficiency of photodissociation . . . . . . . . . . . . . . . . . . . . . . . . . . 118

7 Stimulated Raman transfer into 3 ∆1

120

7.1

Basics of stimulated Raman transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . 121

7.2

Estimation of Raman transfer parameters . . . . . . . . . . . . . . . . . . . . . . . . 125
7.2.1

Strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

7.2.2

Estimation of

1 Π |d| 1 Σ+
1from an LIF measurement of the 1 Π1 lifetime . . 127

7.2.3

Estimation of

1 Π |d| 1 Σ+
1from LIF measurements of the saturation fluence 129

7.2.4

Estimation of 3 Π0+ lifetime and Rabi frequencies for Raman transfer . . . . . 130

xi
7.3

Experiment setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132

7.4

Rabi frequency calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

7.5

Results of stimulated Raman transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
7.5.1

Spectroscopy of hyperfine levels in 3 ∆1 (ν = 0, J = 1) . . . . . . . . . . . . . . 139

7.5.2

Stark spectroscopy with a rotating bias field . . . . . . . . . . . . . . . . . . . 143

8 Ramsey spectroscopy of the eEDM-sensitive transitions [50]

148

8.1

3∆

8.2

Experimental tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

1 levels with rotating bias fields. . . . . . . . . . . . . . . . . . . . . . . . . . . . 149

8.2.1

Rotating magnetic field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

8.2.2

Optical pumping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

8.3

Ramsey spectroscopy at B = 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155

8.4

Ramsey spectroscopy at B 6= 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

8.5

Sign of magnetic g-factor

8.6

A preliminary eEDM measurement and some implications for sensitivity to systematics164

8.7Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167

Bibliography

Appendix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161

171

TablesTable
2.1

Summary of molecular constants for observed transitions . . . . . . . . . . . . . . . . 23

3.1

Orientation of Rydberg HfF and HfF+ ions . . . . . . . . . . . . . . . . . . . . . . . 52

4.1

Comparison of secular, RF micromotion and rotating field circular micromotion . . . 61

4.2

MCP transfer matrix elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

5.1

Fluorescence collection efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92

5.2

Franck-Condon overlaps for ideal transitions to be used with cavity-enhanced transmission. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

6.1

Optics setup for a photodissociation survey scan experiment . . . . . . . . . . . . . . 105

7.1

Calculated electronic transition dipole matrix elements in HfF+ . . . . . . . . . . . . 127

7.2

Measured and calculated energies of electronic states in HfF+ . . . . . . . . . . . . . 129

7.3

Estimation of parameters for stimulated Ramant transfers . . . . . . . . . . . . . . . 132

Figures

Figure1.1

What is the eEDM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2

1.2

Motivation for an eEDM search . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4

1.3

Generic measurement of the eEDM . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6

1.4

Figure-of-merit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6

1.5

3∆

1.6

State manipulations necessary to perform an eEDM search in HfF+ . . . . . . . . . . 14

2.1

Schematic of REMPI experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.2

Collection of raw REMPI data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.3

REMPI spectrum of excited HfF states near 30000 cm−1 . . . . . . . . . . . . . . . . 21

2.4

Isotope shifts and calculated electronic energies for observed neutral HfF transitions

2.5

Rotational line strengths affected by interference between parallel and perpendicular+
1 levels in HfF. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127transition moments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.6

Hypotheses for the observation of large isotope shifts . . . . . . . . . . . . . . . . . . 32

2.7

Isotope shifts as a function of the isotopologue reduced masses . . . . . . . . . . . . 33

2.8

OODR autoionization spectra for two different intermediate states . . . . . . . . . . 34

3.1

Schematic of OODR-LIF experiment conducted on a molecular beam . . . . . . . . . 40

3.2

Energy levels involved in performing OODR-LIF . . . . . . . . . . . . . . . . . . . . 41

3.3

OODR autoionization spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

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3.4

Post-autoionization ion rotational distributions . . . . . . . . . . . . . . . . . . . . . 50

3.5

Post-autoionization ion M + -populations . . . . . . . . . . . . . . . . . . . . . . . . . 52

4.1

Ion trap basic concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

4.2

eEDM ion trap design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

4.3

Ion trap driver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

4.4

Layout of apparatus for ion production and trapping . . . . . . . . . . . . . . . . . . 69

4.5

Ion cloud slosh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

4.6

Extracting MCP transfer matrix elements . . . . . . . . . . . . . . . . . . . . . . . . 76

4.7

Axial patch charges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

4.8

Radial patch charges and micromotion . . . . . . . . . . . . . . . . . . . . . . . . . . 80

4.9

Axial trap anharmonicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

4.10 Rotating electric field inhomogeneity . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
5.1

Light pipe and PMT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

5.2

Ways to reduce scattered light

5.3

LIF frequency scan and readout signal lifetime . . . . . . . . . . . . . . . . . . . . . 93

6.1

Molecular potentials for direct dissociation . . . . . . . . . . . . . . . . . . . . . . . . 102

6.2

Predissociating molecular potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103

6.3

Layout of possible photodissociation lasers . . . . . . . . . . . . . . . . . . . . . . . . 106

6.4

Detection of dissociated Hf+ ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

6.5

Suppression of aboriginal Hf+ ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

6.6

REMPD spectroscopy of HfF+ transitions at around 35000 cm−1 . . . . . . . . . . . 113

6.7

Depletion spectroscopy performed with photodissociation . . . . . . . . . . . . . . . 115

6.8

Photodissociation resonance at around 72000 cm−1 . . . . . . . . . . . . . . . . . . . 117

6.9

Saturation of photodissociation transition with 266 nm pulse energy . . . . . . . . . 118

7.1

Bare states and dressed states in a three-level system . . . . . . . . . . . . . . . . . . 122. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

xv
7.2

1 Π lifetime1

7.3

Calibration of Rabi frequencies for transitions out of the 1 Σ+ state . . . . . . . . . . 137

7.4

Calibration of Rabi frequencies for the 3 Π0+ ← 3 ∆1 transition . . . . . . . . . . . . . 138

7.5

Hyperfine spectroscopy in the 3 ∆1 state . . . . . . . . . . . . . . . . . . . . . . . . . 139

7.6

Stimulated Raman transfer efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . 141

7.7

Effect of parity selection rules on stimulated Raman transfer efficiencies . . . . . . . 142

7.8

Effect of parity selection rules on Stark-shifted peak intensities . . . . . . . . . . . . 145

7.9

Stark spectroscopy of the 3 ∆1 state . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147

8.1

3∆

8.2

Magnetic field coils for a static radial magnetic field gradient . . . . . . . . . . . . . 154

8.3

Measurement of the zero-B-field splitting . . . . . . . . . . . . . . . . . . . . . . . . 158

8.4

Measurement of the magnetic g-factor . . . . . . . . . . . . . . . . . . . . . . . . . . 162

8.5

Sign of the magnetic g-factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165

8.6

Ramsey fringe coherence time and 3 ∆1 lifetime . . . . . . . . . . . . . . . . . . . . . 168. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128+
1 levels in HfF with a rotating quantization axis

. . . . . . . . . . . . . . . . . . 151

Chapter 1
Introduction

1.1

Motivation for an electron electric dipole moment (eEDM) search
The electron is a fundamental particle of mass me , charge −e and spin S = ~/2. The

electron spin and charge give rise to a magnetic moment µe = ge µB S/~, where µB = e~/(2me ) is
the Bohr magneton and ge is the magnetic g-factor. According to relativistic quantum mechanics
as described by the Dirac equation, ge = 2. Quantum electrodynamics (QED), however, predicts
that g e deviates slightly from 2, i.e.
 α 2
α
ge
+ C4
+ ...
= 1 + C2
2
π
π

,

(1.1)

where α is the fine-structure constant, the coefficients Cn are calculated from the QED Feynman
diagrams of order n depicting an electron being scattered by a static magnetic field [14]. A precise
measurement of the electron magnetic g-factor provides a stringent test on QED; in fact, with thecurrent precision on the g-factor to 13 decimal places [33], QED has been tested out to the eighth4order term C8 απ in Eq. (1.1). [2, 3].

What about an electron electric dipole moment (eEDM)? If the center of mass and center ofcharge of the electron are slightly displaced (see Fig. 1.1), the displacement would give rise to an
eEDM. Such a permanent electric dipole moment is fundamentally different from that induced by afinite external electric field, for example in a polar molecule like OH. In this thesis, we only consider
the case where the eEDM points only either along or against the direction of electron spin: if theeEDM is to point along a different direction (such that it can be expressed as a linear combination

2of directions parallel and orthogonal to the electron spin), quantum mechanics would have required
additional quantum numbers beyond ms to describe the electron [44].
Spin
Mass

|de|< 1.05 x 10-27 e cm
(Hinds, 2011)

ChargeFigure 1.1: A displacement between the electron’s center of mass and center of charge gives theelectron an electric dipole moment.

To date, no eEDM has been observed. More precisely, the current experimental limit on
the eEDM is |de | < 1.05 × 10−27 e cm [36]. The observation of an eEDM would have profound
implications on both fundamental symmetries and grand unified theories of physics. Fig. 1.2a illustrates how the presence of an eEDM implies a direct violation of both time-reversal (T) symmetry
and parity (P) symmetry. Under time-reversal (parity inversion), the electron spin (eEDM) flips
direction while the eEDM (electron spin) remains unchanged. In either operation, the relative
direction between the spin and EDM are different compared to the initial configuration, implying
direct T and P violation. By the CPT theorem, direct T violation implies CP violation and viceversa. While CP violation has already been observed in neutral kaon decay in 1964 [13], direct T
violation has only been observed in the B 0 meson decay experiment as recently as 2012 [47]. The
observation of an eEDM would be another experiment that directly confirms the violation of T
symmetry.
As explained above, the eEDM arises from CP violation. In the Standard Model, the CPviolating terms are calculated to be so small that the eEDM is predicted to be < 10−38 e cm[70]. CP- and T-violating terms in the Standard Model also predict that the amount of matterand anti-matter in the early universe should have been approximately equal, in which case thetwo kinds of matter should annihilate such that the universe has almost no remaining matter.

3
Nevertheless, the fact that there is an asymmetry between the amount of matter and anti-matterin the universe is one of the key weaknesses of the Standard Model. Theories beyond the Standard
Model (e.g. supersymmetry) allow for CP-violating terms of much larger magnitudes than that in
the Standard Model. These theories predict an eEDM in the range of 10−29 –10−26 e cm [9, 7, 69].
If we can probe eEDM more precisely at a level that is one to two orders of magnitude beyond thecurrent experimental limit, we can either validate or constrain more rigorously the various theories
beyond the Standard Model (Fig. 1.2b). Of note is the fact that the electric dipole moment of
the electron as predicted by the Standard Model is several orders of magnitude smaller than thatpredicted by the other extension theories. Such a low “Standard Model background” facilitates thediscrimination of these extension theories from the Standard Model should an eEDM be observed.

1.2

Measuring the eEDM

1.2.1

Figure-of-merit

How would one measure the eEDM? In the presence of an external electric field E andmagnetic field B, the Hamiltonian for an electron with eEDM de is:
He (E, B) = − (de E + µe B) ·

σ
|σ|

.

(1.2)

The frequency difference between an electron in its state of spin-down versus spin-up (and assuming
de aligned parallel to the spin) is then given by2
ωe (E, B) = − (de E + µe B) .
~

(1.3)

The measurement of the transition frequency between the spin-up and spin-down states is known
as electron spin resonance (ESR) spectroscopy. To attribute the ESR frequency to de only, theelectron spin-flip frequency is measured with a fixed external magnetic field and the external electricfield E first applied parallel to B and then anti-parallel to B. The difference in the two measured
frequencies then gives 4de E (Fig 1.3a). (One may question the necessity of applying a magnetic field
to measure de ; after all, the electron frequency shift from de can be obtained from only reversing

4

_
+

(a)

+
_

P

de

S

+
_

T
de

S

S

de

-38

10

Hinds (2011)

(b)

-26

10

-28

10

-30

10

-32

10

-34

10

-36

10

10

-40

de [e cm]
SUSY
Left-Right
Multi-Higgs

Standard
Model

Figure 1.2: (a) The presence of an eEDM implies the direct violation of time reversal (T) symmetry
and parity inversion (P) symmetry. As depicted, under either time reversal or parity inversion, theelectron’s spin and eEDM change from being anti-aligned to aligned. Although the electron spinand eEDM are illustrated to be initially anti-aligned, the same argument of T and P violation
holds if the electron spin and eEDM are initially aligned. (b) Theories extending physics beyond
the Standard Model predict eEDM values much higher than that predicted by the Standard Model[9, 7, 69]. These theories can be tested more rigorously by pushing the current eEDM experimental
limit down by another one to two orders of magnitude.

5
the electric field direction. The magnetic field is useful for biasing the measurement frequency
away from 0 Hz, so that the eEDM shift is insensitive to noise sources near DC.) Conversely, one
may add the two transition frequencies measured in a fixed electric field but with the magnetic
field applied aligned and anti-aligned to E (Fig. 1.3b). Whether the magnetic field or electric field
direction is being reversed, the deliberate change should be performed relatively quickly (so that
one is insensitive to drifts in the other experimental parameters) and is henceforth referred to as a‘chop’. Combining the measured transition frequencies from the four chops, we getωe (E, B) + ωe (E, −B) − ωe (−E, B) + ωe (−E, −B) = 8de E .

(1.4)

The statistical sensitivity of an eEDM measurement is governed by three quantities: themagnitude of the electric field E experienced by the electron spin, the coherence time τ , and the√square root of the number of spin-flip transitions N detected in a given integration time, say, of
one day. Fig. 1.4a–c shows how each quantity affects the eEDM measurement, where the eEDM
measurement is depicted in each of these cases as a chop in only the external electric field direction
and the statistical distribution of measured transition frequencies for a given electric field direction
manifests as a spectral line. Firstly, the higher the electric field E experienced by the electron
spin, the larger the separation between the center of each spectral line. Secondly, the longer thecoherence time of the measurement, the narrower the linewidth of each frequency and the betterthe two spectral lines can be resolved. Thirdly, each spectral line is composed of a large numberof trials detecting the spin-flip transition, each of which is independent and therefore the result
follows a Poisson distribution. The signal-to-noise ratio of each spectral line is hence given by
the square root of the number of spin-flip transitions. The higher the signal-to-noise ratio, the√better the determination of each spectral line center. The combination of E, τ and N forms thefigure-of-merit for determining the statistical limit of an eEDM measurement:
δde =

~
√ .
2eEτ N

(1.5)

6
B

(a)

e

B

e

2dee

| ñ
| ñ

w1

w2

| ñ
| ñ

w2 m B w1

w

e

B

(b)

e

B

e

2dee

| ñ

w1
w2

| ñ

| ñ

w2

-meB

w1
w

meB

| ñ

Figure 1.3: (The eEDM may be determined by measuring the electron spin-flip transition frequency
in the presence of an external electric and magnetic field aligned parallel to each other, and then (a)reversing the direction of the electric field and taking the difference of the two transition frequencies,or (b) reversing the direction of the magnetic field and summing the two transition frequencies.

(a)

(c)

(b)

2dee

ÖN

1/t

w

w

w

Figure 1.4: The eEDM measurement figure-of-merit, which is inversely proportional to the statistical uncertainty on the eEDM, is proportional to (a) the electric field E experienced by the√ electron,(b) the coherence time τ , and (c) the square root of the number of spin flips detected N .

7
1.2.2

HfF+ molecular ions for an eEDM measurement

While the discussion of the eEDM measurement so far focuses on a single unpaired electron,
the eEDM measurement is never carried out on a bare electron, as the application of a large electricfield would invariably cause the electron to fly away. Sandars [72, 73, 74, 75] suggested the useof electrons in atoms and molecules for probing the eEDM, where the valence electron’s energy
level can be shifted by the electric field Eeff induced in the polarized atom or molecule upon theapplication of an external electric field Eext . The induction of an effective internal electric fieldfrom Eext can be accounted for using a loophole of Schiff’s theorem [76, 15], a discussion of which isbeyond the scope of this thesis. For atoms, the scale of the internal electric field goes as the cube of
the nuclear charge times the applied external field Z 3 Eext , such that the electric field experienced
by the unpaired electron of interest can be as high as 72 MV/cm in a heavy atom like thallium[71]. In this case, Eext was already maximized at about 100 kV/cm, above which arcing between
the plates can occur in vacuum. To obtain a higher internal electric field, one would either have to
go to an atom of even higher Z or turn to polar molecules.
max ,For polar molecules, the internal effective electric field saturates at a specific value Eeff

unlike in atoms where the internal electric field continues to be proportional to the applied field
for obtainable laboratory electric fields. The saturation occurs when the applied electric field islarge enough to fully mix adjacent molecular states of opposite parity. In the 2 Σ+ state of YbF,
the closest two states of opposite parity are adjacent rotational levels spaced by ∼ (2π)40 GHz, so
the applied electric field of 10 kV/cm was able to induce an effective electric field of 14.5 GV/cm
but not as large as the maximum possible value of 26 GV/cm [39]. Nonetheless, the effective
electric field obtained was already two orders of magnitude higher than that in thallium. Ideally,
one would like to be able to obtain similarly high an effective electric field with a polar moleculemax more easily and to reducewith an external electric field as small as 10 V/cm, so as to access Eeff

systematic effects from, say, leakage currents from the electric field plates; for this purpose, the 3 ∆1electronic state, present in a class of molecules such as ThO [55, 87], WC [46], HfF+ and ThF+

8[56, 62, 55, 45], is a suitable candidate. The 3 ∆1 configuration in those species comes from ans and a d valence electron. The diffuse d electron gives rise to an Ω-doublet of opposite parity
levels spaced as closely as (2π)1 MHz, such that as little as 2 V/cm is required to fully polarize themolecule. The s electron experiences relativistic effects near the nucleus of the heavy atom (e.g.
Th, W, Hf), such that once the molecule is polarized, the internal electric field can be as high as
90 GV/cm!
Of the molecules with the 3 ∆1 state, some are neutral molecules whereas others are molecularions. Trapping neutral molecules is difficult to date, so all the eEDM neutral molecule experiments
work with molecular beams. The coherence time of the eEDM measurement is then limited tothat taken for the molecules to traverse the electric field plates (i.e. ∼1 ms). Molecular ions, on
the other hand, can be easily trapped with electric fields in an ion trap. It is fortuitous that themolecular ions proposed for the eEDM measurement such as HfF+ and ThF+ tend to have 3 ∆1lifetimes of at least three orders of magnitude longer than 1 ms, so we can take advantage of theion trap to perform an eEDM with much longer coherence times (∼300 ms) than for the neutral
molecules. The downside to using molecular ions, however, is that the density of molecular ionstends to be limited by space-charge repulsion between multiple ions, so the number of spin-flip
transitions in an eEDM experiment can be orders of magnitude smaller for molecular ions than for√neutral molecules. Since the eEDM figure-of-merit is proportional to Eeff τ N , for similar effective
electric fields, there is no obvious winner between neutral molecules and molecular ions, and each√experimental group simply has to work as hard as they can on both τ and N to achieve the better
statistical sensitivity!
For this thesis work, the species of choice is the molecular ion HfF+ . Among the different
eEDM experimental groups, the JILA group is the only one employing molecular ions. Beyond a
discussion of the statistical limit to de , molecular ions have the advantage that the longer τ leads
to a narrower spectral linewidth, which makes us less vulnerable to systematic errors that affectthe lineshape.
Fig. 1.5a–c shows the 3 ∆1 , ν = 0, J = 1 energy level structure for 180 Hf19 F for three different

9cases: (a) in the absence of any external fields, (b) with an external electric field but ignoring
the effect of an eEDM, and (c) with both an external electric and magnetic field and accounting
for the eEDM. Since the nuclear spin of fluorine is 1/2 and 180 Hf has no nuclear spin, the J = 1
rotational level has two hyperfine levels, F = 3/2 and 1/2. Without any external fields, the states of√well-defined parity are given by |±i = (|Ω = +1i ± |Ω = −1i)/ 2. For F = 3/2, each state of welldefined parity has four degenerate levels, which are the four mF projections of the hyperfine angularmomentum onto a quantization axis. In the eEDM experiment, the external electric field serves as
the quantization axis. When present, the external electric field mixes the states of opposite parity
to give states where Ω, which is the total projection of orbital and electron spin angular momentum
onto the internuclear axis n̂, is a good quantum number. The F = 3/2 and 1/2 levels split into fourand two Stark manifolds, respectively, while states of the same mF Ω remain degenerate. Finally,in the presence of an external magnetic field colinear with the external electric field, the stretch
states of the same mF Ω in the F = 3/2 hyperfine level are split by the frequencies

u/ℓwhere gF

ω u = 3gFu µB B + 2de Eeff ,(1.6a)

ω ℓ = 3gFℓ µB B − 2de Eeff ,(1.6b)

is the magnetic g-factor of the upper and lower Stark manifolds. The sign of the eEDM

transition frequency shift can be understood as the following: for the upper manifold {|ai , |bi}, theeffective electric field points parallel to B. Assuming that de is aligned with the electron spin, state|ai (|bi), which has been shifted upwards (downwards) by the Zeeman effect, is displaced further up(down) by the effective electric field, giving an extra energy splitting of 2de Eeff on top of the usual
Zeeman splitting. Conversely, for the lower manifold {|ci , |di}, Eeff points in the opposite direction
as B. The sign of the energy splitting 2de Eeff is then opposite to that of the Zeeman splitting. The
magnetic g-factors of the upper and lower Stark manifolds are predicted to be very similar, suchthat a chop of the electric field amounts to performing the electron spin resonance on the upper
versus lower Stark manifold. The ability to sample the magnetic field using the same molecularspecies as a co-magnetometer is another advantage of using an Ω = 1 level such as the 3 ∆1 level10[18, 23]. Analogous to Eq. (1.4), the eEDM signal is then given by the four-way chop:ω u (Eext , B) + ω u (Eext , −B) − ω ℓ (Eext , B) + ω ℓ (Eext , −B) = 8de Eeff .

(1.7)

In HfF+ , Eeff saturates at 24 GV/cm [62]. From Eq. (1.7), a determination of de at the levelof 1 × 10−28 e cm — about an order of magnitude better than the present experimental limit —then demands that the sum frequency shift of 8de Eeff be measured to as precisely as (2π)5 mHz!
At this point, three commonly asked questions may arise in the reader’s head:(1) How does one measure such a small frequency shift as (2π)5 mHz?
(2) How does one experimentally determine Eeff ?
(3) How can one, in the first place, apply an external bias electric field without ejecting the
HfF+ ions from their ion trap?
The answer to the first question is that the absolute frequency to be measured in any given
chop of Eeff and B is only ω u /(2π) ≈100 Hz, and for an estimated spectral linewidth of 2 Hz, thespectral line center only needs to be determined to a precision of 1/2000 to measure a shift of of theline center by 1 mHz. The absolute frequency measurement for a particular chop is in turn given
by Ramsey spectroscopy. Instead of using a narrow laser or radiofrequency source to probe theeEDM transition (say, ω u ), we first populate all the ions in |ai (with none in |bi). We then apply
a π/2 pulse to create an equal superposition of the two stretch states (i.e. |bi + |ai), wait for someuduration T over which |ai dephases relative to |bi (i.e. |bi + e−iω T |ai), and finally apply another
π/2 pulse to read out the relative phase ω u T as a fraction of ions in state |ai. As T is varied suchthat the relative phase changes from 0 to 2π, the final fraction of ions in state |ai oscillates from 0
to 1, and the frequency of oscillation then gives ω u .
The need to obtain a reliable value for Eeff is important because de can only be extracted
from a measured frequency after having knowledge of Eeff . All the values for Eeff for the different
molecules listed earlier in this chapter come from ab-initio calculations of the molecular potentials,
which therefore motivates the second question. Unfortunately, there is no way to experimentally

11

(c)

(b)

(a)
F=1/2

|-ñ
|+ñ

-

-

F S =-1

F S =+1n̂Hf|-ñ
F=3/2 |+ñmF = -3/2 -1/2

Hf

|W = +1ñ

wef

1/2 3/2n̂2+eext B

Hf

2+

Hf

2+

n̂

eext Bn̂

S = +1-F|W = -1ñ

mF = -3/2|bñ

d e eff+2 e|añ|W = -1ñ

2+

-

eeff

B
B
u 3g FmW=

S = -1F|W = +1ñ

-1/2

1/2

3/2

l

eeff

d ee effm BB - 2

|cñ

1/2

3/2

W =3g F|dñ

mF = -3/2-1/2

Figure 1.5: HfF+ energy levels within the 3 ∆1 , ν = 0, J = 1 state. This figure is adapted from[45], with the energy ordering of the hyperfine levels switched to reflect the results experimentallyobtained in this thesis. (a) In the absence of an external electric field, each hyperfine level possesses
two closely-spaced states of opposite parity {|+i , |−i}, while the hyperfine mF projections aredegenerate. (b) With an external electric field (that also sets the quantization axis), the states of
opposite parity are mixed and the hyperfine levels are split into (2F + 1)/2 Stark manifolds, where
the molecule internuclear axis n̂ is aligned parallel (anti-parallel) to the external electric field forthe lower (upper) Stark manifold. (c) In the presence of a magnetic field parallel to Eext , the mF
sublevels undergo a Zeeman shift. The eEDM-sensitive transitions are denoted by ω u/ℓ , with theeEDM having oppositely signed contributions to ω u and ω ℓ (see text).

12
measure Eeff . For the case of YbF, several different calculations were performed to obtain Eeff ,amongst which the agreement was valid to within 10% [39]. The 10% error on Eeff ultimately had
almost no bearing on the eEDM result reported [36]. For HfF+ , we hope to check the validity of theab-initio calculations by measuring other important experimental parameters such as the hyperfine
structure of 179 Hf19 F and 177 Hf19 F and comparing against the predicted values, thereby indirectly
giving confidence to the calculated value of Eeff .
The issue raised by the last question comes from the fact that a DC bias electric field iseither smaller than the trapping fields, such that the HfF+ ions will simply be displaced to a newposition in the trap, or larger than the trapping fields, such that the HfF+ ions will be ejected fromthe trap. For a bias field of Eext =10 V/cm, the latter case applies. The trick is to apply the bias
electric field in a rotating manner, where the rotation frequency ωrot is fast enough for the ions toremain trapped but slow enough for the ions’ internuclear axis to track the electric field direction
adiabatically. In fact, the application of a rotating quantization axis is unique to our experimentamongst trapped ion experiments.

1.2.3

Challenges of using HfF+

Unlike atoms, molecules have many more quantum states: besides electronic, hyperfine andZeeman sublevels, molecules also have vibrational and rotational levels. As explained in the description of the Ramsey time-of-flight spectroscopy, full quantum control of the Zeeman-hyperfinerovibronic states of HfF+ is needed to carry out the eEDM measurement. The implementation ofquantum state preparation, state manipulation and state readout at the level of (2π)100 Hz wascomplicated by the fact that no spectroscopic information on HfF+ was available when our experiment first began. Some theoretical calculations of the low-lying states were performed [62, 63],
but those had uncertainties as large as 30 THz (i.e. 50 nm uncertainty for a transition centered at
700 nm), such that theorists could not agree on whether the ground state of HfF+ was 1 Σ+ or 3 ∆1[54]. There was a lot of work to do!
In general, spectroscopy of molecular ions is a lot more challenging than spectroscopy of

13
neutral molecules because of the much lower density (by three orders of magnitude in typicalsetups) of molecular ions. Along our journey towards precision spectroscopy of HfF+ in the 3 ∆1state, we were fortunately aided by the low-lying electronic state assignments that came out of
Heaven et. al.’s experiments [4] and by a parallel JILA experiment performing velocity modulation
spectroscopy in a discharge tube [82, 16].
Beyond assigning the energy levels, we had to create a large fraction of HfF+ ions in a single
desired quantum state. While a high ion number was important to increasing the spin-flip detection
count rate, more ions also meant more ion-ion collisions that could also lead to decoherence on
our Ramsey measurements, so efficient state preparation was key to maximizing the former while
minimizing the latter constraint. One method to state-selectively create HfF+ was to photoionize
neutral HfF using two resonant photons, which meant that we needed to first find the ionizationenergy of neutral HfF as well as vibronic states of neutral HfF that could serve as intermediate
states for two-photon photoionization. The eEDM-sensitive transitions lay in the 3 ∆1 metastablestate, so special effort (such as combining photoionization with stimulated Raman transfer) was
needed to populate that electronic state.
For state detection, a popular atomic physics technique is laser-induced fluorescence (LIF),
where the number of fluorescence photons is proportional to the number of molecular ions excitedby a laser addressing a particular transition. Unlike atoms, molecules generally have no cyclingtransitions, which makes LIF a rather painful way of probing the molecules. Photodissociation,
where the HfF+ molecule is state-selectively broken up into Hf+ and a fluorine atom, promised amuch higher detection efficiency by counting ions. However, to enable photodissociation as a state
readout technique, we had to perform UV spectroscopy of high-lying bound and dissociating statesof HfF+ in our ion trap.
Finally, the manipulation of molecular ions with a rotating bias electric field meant non-trivial
physics to be explored, which was in itself a very happy problem to have, since it finally signified
our departure from “shot-in-the-dark” survey spectroscopy!

14

DissociatingstatesHf+ + F

(d)
(c)
(b)

Neutral
HfF

D1

3

(a)

+

XS
1

Energy levels of HfF+
Figure 1.6: Major state manipulation steps that had to be performed to enable to eEDM measurement: state preparation of HfF+ in a single desired quantum level using (a) photoionizationand (b) Raman transfer, and state detection using either (c) laser-induced fluorescence or (d)photodissociation. This figure has been adapted from [81, 16].

15

1.3

Overview of thesis
Unlike many physics theses, there is no single “experiment setup” chapter that can ade-quately summarize the experiment setup used in this thesis work. From neutral HfF molecules
to a molecular ion beam to trapped molecular ions, the experiment setup is constantly changing (with many vacuum breaks!) and is thus described in its appropriate chapter. Chapter 2
presents the spectroscopy of neutral HfF performed using resonance-enhanced multiphoton ionization (REMPI), with the goal of identifying suitable vibronic states at 30000–33000 cm−1 that canbe used as intermediate states in two-photon autoionization to create HfF+ . The state-selective
nature of two-photon autoionization is probed by performing LIF on a beam of HfF+ ions, as described in chapter 3, where we show that as much as 30% of the total ion yield can be formed in aparticular |J, mJ i state. For the remainder of the thesis, the HfF+ ions are trapped in a radiofrequency Paul trap, whose design and associated electronics particular to the eEDM experiment are
given in chapter 4. Chapter 4 also discusses various techniques that have been used to characterize
the ions’ in-trap behavior. Chapter 5 revisits the implementation of LIF, this time with trapped
HfF+ ions. Beyond chapter 5, we abandon LIF as a technique for state detection and turn insteadto photodissociation, for which the spectroscopy of high-lying HfF+ states and usefulness of photodissociation as a readout tool are illustrated in chapter 6. In chapter 7, the stimulated Raman
transfer of HfF+ ions from the ground 1 Σ+ state to the desired quantum states in 3 ∆1 is described,
and we experimentally map out, for the first time, the level structure presented in Fig. 1.5a–b.
Finally, chapter 8 discusses the implementation and physics of coherent Ramsey spectroscopy withtrapped HfF+ ions in a rotating bias field and closes with a preliminary measurement of the eEDM
at the 10−25 e cm level.

Chapter 2
REMPI spectroscopy of neutral HfF [51]The first stage of preparing HfF+ ions in a single desired ro-vibronic level is to state-selectively
autoionize neutral HfF prepared using the optical-optical double resonance (OODR) technique [52].
In OODR, two ultraviolet (UV) photons of different frequencies are used, where the first photon
is tuned to an intermediate state of neutral HfF and the second photon further excites HfF toa Rydberg state above the lowest ionization threshold at 59462(2) cm−1 [4, 52]. Since the final
state of the autoionized product depends strongly on the intermediate state accessed by the first
UV photon, there is a need to characterize and understand the neutral HfF states that lie in thevicinity of and above 30000 cm−1 , some of which may hold promise as intermediate states for HfF+
ion-creation in the desired 3 ∆1 state.
The HfF spectroscopy published to date includes transitions to excited states as high as
28600 cm−1 , detected by laser-induced fluorescence [1, 30], and resonance-enhanced multi-photon
ionization (REMPI) [4].

This chapter1

presents HfF spectroscopy performed in the 30000–

33000 cm−1 range, using both 1+1 REMPI and 1+1′ REMPI, which complements the previously
published spectroscopic results.

2.1

Experiment setup
Figure 2.1 shows a schematic of the experimental setup used to ionize a HfF molecularbeam via (1+1) REMPI. The source and time-of-flight mass spectrometry (TOFMS) chambers are
1

Most of this chapter has already appeared in Reference [51].

17

Pulse
valve

UV ionization laser

HfF

Ablated Skimmers
Hf target

A
B C
TOFMS

MCP
dcab abcd cadb abcd abcd abcd
abcd abcd abcd abcd abcd
abcd abcd abcd abcd abcd abcd
abcd cadb abcd cadb abcd
Hf+abcd abcd abcd abcd abcd cadb
Fabcd cadb abcd abcd abcd
abcd cadb abcd cadb abcd cadb
abcd abcd abcd abcd abcd
abcd cadb abcd abcd abcd cadb
abcd abcd abcd abcdAmplifier
cadb
abcd abcd abcd abcd abcd abcd
cadb abcd cadb abcd cadb

Oscilloscope
Ions (a.u.)Ablationlaser
Ne (99%),SF 6 (1%)

2

2.2

2.4

2.6

Time (us)

(a)

(b)

180Hf19F

2.4

179Hf19F

2.6

Oscilloscope

2.2

178Hf19F
177Hf19F

2

176Hf19F

Time (us)Arrival time

Figure 2.1: Schematic of the resonance-enhanced multiphoton ionization (REMPI) experiment.

32800

32825

32850

Ions (a.u.)

Ions (a.u.)

Laser frequency (cm-1)

Ions (a.u.)

( c)

32800
32825
Laser frequency (cm -1)

32850

Figure 2.2: (a) A pictorial summary of the oscilloscope traces taken over multiple vibronic bands.
(b) A sample of the oscilloscope trace shows the capability of the time-of-flight mass spectrometry(TOFMS) apparatus to separate the spectra arising from each of the five isotopologues of HfF+ .
(c) (1+1) REMPI spectrum of 178 Hf19 F.

18separately pumped. A gas comprising 1% SF6 and 99% Ar is released into the source chamber
through the opening of a pulsed valve (800 µm orifice, 120 psi backing pressure) for 150 µs. In thepresence of SF6 , the ablation of a Hf rod by the fundamental of a Nd:YAG pulsed laser (5–7 ns,
25 mJ/pulse, focused beam diameter 230 µm) creates HfF. We can also use the second harmonicof the Nd:YAG laser to perform the ablation; both cases gave no difference to the number of HfF
molecules created. The HfF molecular beam is cooled through supersonic expansion to a rotationaltemperature of ∼ 10 K. The beam is collimated by two skimmers (1 mm orifice diameter, separation
distance 29 cm) before passing through a home-built TOFMS, which is a series of six disks arranged
along a common axis [83].
In the TOFMS chamber, a UV laser, tuned such that two photons are required to ionize
HfF, intersects the molecular beam perpendicularly in the TOFMS region A. The resultant HfF+
ions drift under an electric field of 1 V/cm toward region B. Regions B and C of the TOFMS are
operated in the Wiley-McLaren mode [88]: when in region B, the ions are spatially focused by asmall electric field of 0.25 V/cm until they reach region C, in which the ions are velocity-focused,by a transient electric field of 1 kV/cm for 500 ns, toward a microchannel plate assembly (MCP)
positioned 56 cm away. The ion signal is enhanced by a transimpedance amplifier and read out
by an oscilloscope. The TOFMS has a fractional mass resolution of at least 1/200, allowing us
to resolve individual isotopologues of HfF+ that differ by 1 amu (natural relative abundances inparentheses): 176 Hf19 F (5.2%), 177 Hf19 F (18.6%), 178 Hf19 F (27.3%), 179 Hf19 F (13.6%) and 180 Hf19 F(35.1%). Figure 2.2(a) gives a pictorial summary of all the oscilloscope traces recorded over multiple
vibronic bands, while Fig. 2.2(b) shows a sample of an oscilloscope trace for a particular wavelengthof the UV laser. All five isotopologues of HfF+ , well-separated in arrival time on the MCP, appear
as laser frequency striations of different intensities.
As detailed in Ref. [52], cold (∼ 10 K rotational temperature) HfF molecules are created byablating a Hf target in the presence of 1% SF6 and 99% Ne (690 kPa backing pressure), followed bysupersonic expansion through a 800 µm diameter nozzle. The molecular beam is collimated by two
1 mm diameter skimmers separated by 29 cm before passing through a home-built time-of-flight19
mass spectrometer (TOFMS), which is a series of six disks arranged along a common axis [83].
Most of the HfF spectra presented in this chapter are recorded using (1+1) REMPI, in
which the spectral resolution is limited to 0.1 cm−1 (FWHM), the linewidth of the UV laser. The
UV photoionization radiation comes from a 532 nm-pumped dye laser operating with DCM dye,frequency doubled in a KDP crystal (100-200 µJ/pulse, 10 ns, 0.1 cm−1 FWHM). Its wavelength
is continuously monitored by a wavemeter calibrated against Ne spectral lines.
Two of the HfF vibronic bands are recorded with high spectral resolution (0.003 cm−1 )using (1+1′ ) REMPI, where two co-propagating laser pulses simultaneously intersect the molecularbeam at the same intersection point. The first photon (3 µJ/pulse, 10 ns, 150 MHz FWHM) is thefrequency doubled output of a home-built two-stage Rhodamine 101 dye cell amplifier. The dye cell
amplifier is seeded by a continuous-wave ring dye laser operating with Rhodamine 610 Chloride dye.
It is pumped by the second harmonic of a Nd:YAG laser. The seed laser frequency is monitored bya high-precision wavemeter that is regularly calibrated against the 87 Rb D2 transition. The second
photon in (1+1′ ) REMPI, held at a fixed wavelength of 351.5 nm, is provided by the same dye laser
as that used in the (1+1) REMPI setup, but operating with LDS722 dye.
In this chapter, transitions between energy levels of HfF are labeled as {ν0 /103 }, where ν0 is
the vibronic band origin in cm−1 [5].

2.2

HfF spectra in the range 30000–33000 cm−1
A survey scan of HfF transitions was conducted over the frequency range 30000–33000 cm−1

(Fig. 2.3(a)), which is the range encompassed by the frequency doubled output of the DCM dye.
Most of the strong transitions were scanned in detail and were found to belong to either an Ω′ =3/2 ← Ω′′ = 3/2 transition (Fig. 2.3(b)) or a Π1/2 ← Ω′′ = 3/2 transition (Fig. 2.3(c)).
The REMPI spectra were modeled by the following Hamiltonian for the Ω = 3/2 states [35]:E(J) = Te + Gν + BJ(J + 1) ,(2.1)

where Te is the electronic energy (difference in energy between the extrapolated minima of the

20
X 2 ∆3/2 and electronically excited states) and Gν is the energy of the vibrational level ν. For theΠ1/2 states, there is strong Λ-doubling and transitions from the Λ-doubled X 2 ∆3/2 ground state
into both Λ-doublets of a given rotational level can be resolved, even in the low-resolution spectra.
Since no prior information is known about the parity of a given member of a Λ-doublet, the doublets
are assigned ‘a’/‘b’ instead of the usual spectroscopic notation ‘e’/‘f ’ [11]. Their energy levels canbe modeled by the following polynomial [48]:
E

a/b



1
1
(−1)(J+ 2 )(p + 2q) J +.
(J) = Te + Gν + BJ(J + 1)−/+
2
2

(2.2)

Following Ref. [1], we assume that the 2 Π spin-orbit splitting is large enough for us to consider
DE
only the diagonal matrix element 2 Π1/2 |H|2 Π1/2 in our description of the Λ-doublets. Amongthe Π1/2 states, the 4 Π1/2 states can borrow oscillator strength from the 2 Π1/2 states via spin-

orbit coupling. Since transitions into the 4 Π1/2 upper levels would look very similar to those into2Π
1/2 , we have left out the superscript in the term symbol for the Π1/2 levels.

Based on the Λ-

doubling, none of the observed spectra belong to excited states of Σ character, which have beenpreviously reported in the ranges 13800–14400 cm−1 [30] and 19700–20000 cm−1 [1]. For both
Π1/2 and Ω′ = 3/2 types of excited electronic states, the centrifugal distortion term, DJ 2 (J + 1)2 ,is neglected because the supersonic HfF molecular beam is too cold to populate rotational levels
beyond J = 21/2, which would be required for an accurate determination of D.
Although all five isotopologues were observed, only the two most abundant (178 Hf19 F and
180 Hf19 F) were analyzed. (In Section 2.5, we extend for selected bands our analysis to the 177 Hf19 F

and 179 Hf19 F isotopologues.) For a given transition, the two isotopologues’ REMPI spectra aresimultaneously fit to a contour described by a common set of fit parameters: temperature, intensity,
band origin for 180 Hf19 F (180 ν0 = 180 Te′ − 180 Te′′ + 180 G′ν ′ − 180 G′′ν ′′ ), band origin for 178 Hf19 F(178 ν0 ), lower state rotational constant (B ′′ ), excited state rotational constant (B ′ ) and, whereapplicable, the Λ-doubling constant (p + 2q)/2. Since the rotational constants of a given state forthe two isotopologues are related to each other by the inverse ratio of their reduced masses µ (e.g.,
180 B/178 B =178 µ/180 µ), the B-value ratios are held fixed for the simultaneous contour fit.

The

21

↓↓ ↓↓↓

Ions (a.u.)

(a)
(2)

∗∗

∗

Ions (a.u.)

500

∗
1000

(b)

−6
−4
−2
0
2
4
(First photon energy) − 31886.7 cm−1

∗ ∗

1500
2000
(First photon energy) − 30000 cm−1

(c)

−5
0
5
(First photon energy) − 32980.4 cm−1↓↓↓ ↓ ↓

2500

3000

(d)

−6
−4
−2
0
2
4
(First photon energy) − 32322.7 cm−1

Figure 2.3: (a) Coarse (1+1) REMPI scan of excited HfF states near 30000 cm−1 . The ion signal
shown is the integrated ion signal for all five HfF isotopologues. Two main types of transitions havebeen identified in this survey scan: Ω′ = 3/2 ← Ω′′ = 3/2 (marked by asterisks, typical spectrum
shown in (b)) and Π1/2 ← Ω′′ = 3/2 (marked by arrows, typical spectrum shown in (c)). (b)Detailed (1+1) REMPI scan of the {31.89} vibronic band. The red smooth curve is a contour fit to
the data shown as connected black dots. (c) Detailed (1+1) REMPI scan of the {32.98} vibronic
band. The blue smooth curve is a contour fit to the data shown as connected black dots. (d) High
resolution (1+1′ ) REMPI spectrum of the {32.32} vibronic band. Individual upper state rotational
levels of opposite parity can be resolved.

22
resolution of our data is insufficient to detect a difference between the (p + 2q)/2 terms for different
isotopologues.
The molecular constants for the observed HfF transitions are summarized in Table 2.1. The
numbers in parentheses indicate the 1σ-standard deviation in the last digit. The standard deviationfor each fit parameter was calculated from a histogram of fit parameters obtained by bootstrapping
the residuals of the fit [24]. The bootstrapping process adds the residuals, obtained after a single
fit iteration, randomly to the fitted data to form a new data set, which is then re-fit against
the model; this process is repeated a hundred times to get a hundred sets of fit parameters forthe histogram. For the bands examined in high-resolution (1+1′ ) REMPI scans, (1+1) REMPI
data for the same bands was also available for comparison. We find good agreement between thevalues of ν0 from the coarse (1+1) REMPI spectra and from the (1+1′ ) REMPI spectra, where theuncertainty in ν0 is the specified accuracy of the wavemeter, i.e. 0.1 cm−1 . The global systematic
error of 0.1 cm−1 is determined by how often the wavemeter is calibrated against the Ne spectral
lines. For each vibronic band, because the spectra of all isotopologues are simultaneously recorded,
the isotope shifts from the (1+1) REMPI scans and (1+1′ ) REMPI scans agree well when theerror calculated by the bootstrap method is at least 0.01 cm−1 . Similarly, the uncertainties in
B ′ and B ′′ appear to be dominated by the bootstrap statistics when they are at least as large as
0.001 cm−1 . When the purely statistical standard deviations in the isotope shift or {B ′ , B ′′ } fall
below 0.01 cm−1 and 0.001 cm−1 respectively, the uncertainties reported in Table 2.1 have been
increased to reflect an estimate of the corresponding systematic errors. We find that the purely
statistical uncertainty estimated using the bootstrap method accounts well for the uncertainty inthe Λ-doubling parameter.

2.3

Lower states of observed transitions
From previous work, the electronic ground state of HfF is 2 ∆3/2 and for ν = 0, the rota-

tional constants are B =0.284 001(7) cm−1 and 0.283 668(6) cm−1 for the 178 Hf19 F and 180 Hf19 F
isotopologues respectively [1]. From our own laser-induced fluorescence studies [30], we get theTable 2.1: Summary of molecular constants (all in cm−1 ) for observed transitions. The numbers in parentheses denote the 1σ uncertainties,
assigned as explained in the text.
Ω′

3/2

1/2

180 Te′e27165(74)27307(19)28137(19)31831(19)31833(19)32385(56)27471(19)29565(19)29682(37)29723(37)31276(37)31349(37)31485.1(5)31629(37)31690.0(4)31799(19)

180 ν

0−

178 ν

-1.67(4)-1.838(10)-1.150(10)-0.030(10)-0.335(10)0.00(3)-2.962(12)-1.464(12)-1.43(2)-1.71(2)-0.49(2)-0.81(2)-0.4503(3)-0.62(2)-0.2834(2)-0.553(14)0180 Hf19 F

ν030272.97(10)30731.53(10)30277.59(10)31886.71(10)32466.00(10)32384.89(10)32980.34(10)32282.12(10)32343.44(10)32905.78(10)32188.26(15)32856.7(2)32322.7375(2)32782.57(11)32217.15454(14)32822.37(12)178 Hf19 F

B ′′

B′

0.282(3)0.2864(01)0.2859(10)0.2832(10)0.2852(10)0.2810(10)0.2823(10)0.2849(10)0.2843(10)0.2800(12)0.280(2)0.2841(13)0.28364(2)0.2832(10)0.28378(2)0.2814(10)0.249(3)0.2532(10)0.2596(10)0.2638(10)0.2630(10)0.2625(12)0.2503(10)0.2586(10)0.2623(10)0.2499(12)0.257(2)0.2568(12)0.25667(2)0.2573(10)0.26019(2)0.2553(10)ν030274.63(10)30733.37(10)30278.74(10)31886.74(10)32466.34(10)32384.88(10)32983.31(10)32283.58(10)32344.87(10)32907.5(2)32188.75(15)32857.5(2)32323.1878(2)32783.2(2)32217.43796(14)32822.93(10)B ′′0.283(3)0.2867(10)0.2862(10)0.2835(10)0.2855(10)0.2813(10)0.2826(10)0.2852(10)0.2846(10)0.2803(12)0.281(2)0.2844(13)0.28395(2)0.2835(10)0.28409(2)0.2817(10)B′
0.249(3)0.2535(10)0.2599(10)0.2641(10)0.2633(12)0.2628(10)0.2506(10)0.2589(10)0.2626(10)0.2502(11)0.257(2)0.2571(11)0.25695(2)0.2576(10)0.26047(2)0.2556(10)(p + 2q)/2
0.0735(9)0.0176(6)0.0787(7)0.0159(7)0.057(2)0.054(3)0.04252(3)0.074(2)0.08537(2)0.0879(12)2324isotope-averaged rotational constants to be Bν=0 = 0.2836(4) cm−1 , Bν=1 = 0.2822(10) cm−1 andBν=2 = 0.2791(12) cm−1 . We found [30] that in our apparatus a majority of the HfF molecules are
created in the ground vibronic state, although populations in multiple lower vibrational levels canbe retained, athermally, in the supersonic expansion.
In this chapter, all characterized transitions appear to originate from the 2 ∆3/2 ground stateof HfF. In principle, the vibrational assignment of the lower state can be inferred from a precise
fit to the lower state’s rotational constant and comparison against the values obtained in Ref. [30].
The vibrational quantum number of the lower state was indeed obtained from our high-resolution(1+1′ ) REMPI data (Fig. 2.3(d)), which shows that some bands we observe come from the groundvibronic state. However, the (1+1) REMPI data are too noisy, too broad in linewidth, and have
population in too few rotational states to permit a precise enough determination of B ′′ .

2.3.1

A tool for understanding vibronic bands

The spectra of HfF in the vicinity of 30000 cm−1 are complicated; tools are needed to sortout the spectra and to group together excited states that belong to the same electronic orgin. For
most of the vibronic bands, we did not have available to us sufficiently precise determinations ofboth B ′ and B ′′ to determine the vibrational numbering of upper and lower state levels. Instead,
we used the isotope shift, ∆ν ≡ 180 ν0 − 178 ν0 , to determine an estimate of the electronic energy,Tee′ , for each excited vibrational level.

Assuming that the electronic and vibrational energies are separable, we can write the vibronic

band origin for the isotopologue i Hf19 F as(i)

ν0 = (i) Te′ − (i) Te′′ + (i) G′ν ′ − (i) G′′ν ′′ ,and, assuming an approximately harmonic potential, we can write!
pp(i) µ −
180 µ
180 ′
180 ′
p
Gν ′ − (i) G′ν ′ =Gν ′ ,
(i) µ

(2.3)

(2.4)

where (i) µ is the reduced mass for isotope (i). A similar relation applies for G′′ν ′′ , thus if we define
180 T ′′ ≡ 0, we combine Eqs. (2.3) and (2.4) to give an estimated value of the electronic energy,e25
180 Te :
e

180 e
Te

where η ≡pp

178 µ/(

≡

180

=

180

180 µ −

Te′ − 180 Te′′
ν0 + η ∆ν − 180 Te′ − 178 Te′ + 180 Te′′ − 178 Te′′ ,p178 µ) ≈ 1861.

(2.5)

Then, assuming that the electronic contribution to

the isotope shift is much smaller than the vibrational contribution [35],180 e′
Te = 180 ν0 + η∆ν .

(2.6)

Even in the case that the electronic contribution to the isotope shift (180 Te′ − 178 Te′ − 180 Te′′ + 178 Te′′ )is not much smaller than the vibrational contribution (180 G′ν ′ − 178 G′ν ′ − 180 G′′ν ′′ + 178 G′′ν ′′ ), twobands that share common upper and lower electronic states should get, from Eq. 2.6, very similarvalues for 180 Tee′ , even if ν ′′ and ν ′ are different for the two bands. Again, this depends on theassumption of harmonic potentials and of separable electronic and vibrational contributions to theband energy.
Figure 2.4 is a graphical summary of the observed Ω′ = 3/2 ← X 2 ∆3/2 bands and Π1/2 ←X 2 ∆3/2 bands in HfF. Part (a) of the figure shows the isotope shifts, where an isotope shift isestimated to be about -0.3 cm−1 for a change in vibrational quanta of ν ′ − ν ′′ = +1. Some isotope
shifts of anomalously large magnitude (1.5 cm−1 to 3 cm−1 ) are further discussed in Section 2.5.
Part (b) shows the estimated electronic energy versus band origin, in which transitions that sharethe same pair of lower and upper electronic states are expected to line up horizontally. In Fig. 2.4(b)we see two bands {31.89} and {32.47} that, while their band origins are separated by 579 cm−1 ,have 180 Tee′ values that differ by only 13 cm−1 (identical within measurement uncertainty). It is

likely that these two bands share a common electronic transition with 180 Tee′ ≈ 31840 cm−1 , asindicated by the y-axis. We note that 579 cm−1 would be a reasonable excited state vibrational

spacing. We can see, from the spacing of data points in the y-direction in Fig. 2.4(b), that there
are at least four distinct Ω′ = 3/2 electronic levels: near 27200, 28150, 31850 and 32400 cm−1 .
As a caveat, we note that several of the bands have unreasonably large isotope shifts. We discusspossible causes for anomalous isotope shifts in Section 2.5 below.

26
For the Π1/2 ← X 2 ∆3/2 transitions, from Fig. 2.4(b) we can see immediately that there are
multiple distinct Π1/2 electronic levels: one with 180 Tee′ ≈ 27500 cm−1 , at least one with 180 Tee′ ≈29600 cm−1 , and multiple levels with 180 Tee′ in the range 31500 ± 300 cm−1 . One cannot say forcertain that the three bands with 180 Tee′ ≈ 29600 cm−1 share a common electronic transition. Withreference to Table I, we see the {32.34} band has a Λ-doubling constant quite distinct from that ofthe {32.91} band, which suggests either two distinct electronic transitions or, more likely, a local
perturbation of one of the bands. For the cluster of six Ω′ = 1/2 bands with 180 Tee′ between 31200 and
31800 cm−1 , the spread in 180 Tee′ is too large for the bands to share a common electronic transition.

Moreover, the respective rotational constants for the bands {32.22} and {32.32} are determined so
precisely that we can say with some confidence that these two bands share a common lower levelvibrational level (ν ′′ = 0), but belong to distinct upper vibrational levels. Since the values of ν0
are too close together to make it likely that the upper levels are adjacent vibrational levels of thesame electronic state, it seems quite likely that the two bands terminate in distinct electronic upper
levels. For the bands {32.19} and {32.86}, the vibronic band origins differ by 668.41(14) cm−1 ,which is within 2σ of the 1–0 vibrational energy splitting of the X 2 ∆3/2 ground state [30]. Further,both bands fit to the same B ′ whereas one band fits to a value of B ′′ that is consistently smaller
than that of the other band. This strongly suggests that the bands {32.19} and {32.86} arise fromthe ν ′′ = 1 and ν ′′ = 0 ground vibrational levels, respectively.

2.4

Rotational line strengths
In the (1+1) REMPI experiments, the transition excited by the second photon is typically left

unsaturated, so the observed REMPI line strengths are actually a convolution of the line strengths
for both the first and second step in REMPI. We have observed in other work [52] that the abovethreshold ionization spectrum is highly structured. This structure corresponds to νRyd > 0 levels
that autoionize into ν + = 0 vibrational levels of HfF+ . Qualitatively, the Hönl-London expressionsfor Hund’s case (a) molecules work well to describe the observed rotational line intensities. This is
the case for all observed bands except two Ω′ = 3/2 ← X 2 ∆3/2 bands: {30.73} and {32.47}.

∆ν (cm−1 )

27

0

(a)

−1
−2
−3

(b)

2500
2400
2300
1900
1800
1700

180 f′Te − 30000 (cm−1 )

1600
1500
1400
1300
1200

−200
−300
−400
−500

−1800
−1900
−2500
−2600
−2700
−2800
−2900
−3000

0

500 1000 1500 2000 2500 3000

ν0 − 30000 (cm−1 )Figure 2.4: (a) Isotope shifts (triangles denoting Ω′ = 3/2 ← X 2 ∆3/2 transitions and circles
denoting Π1/2 ← X 2 ∆3/2 transitions) and (b) calculated electronic energies for the Ω′ = 3/2 ←X 2 ∆3/2 transitions (dashed lines terminating on the left axis) and Π1/2 ← X 2 ∆3/2 transitions(dashed lines terminating on the right axis). The spread in 180 Tee′ values indicates at least four
distinct Ω′ = 3/2 electronic states and at least six distinct Π1/2 electronic states.

28
To fit the line intensities in a given vibronic band, we included terms that described possible
interference effects between parallel (Ω′ − Ω′′ = 0) and perpendicular (Ω′ − Ω′′ = ±1) transitions[48]. For example, a nominal Ω′ = 3/2 (for clarity, also denoted here as Ω′N ) excited state could
also possess some Ω′ = 1/2 (= Ω′N − 1) and/or Ω′ = 5/2 (= Ω′N + 1) character from mixing (viathe Hamiltonian term -BJ∓ L± ) with nearby “dark” states. When the excited state is no longer agood Hund’s case (a) state due to these admixtures, transitions between the 2 ∆3/2 ground state
and all three admixed Ω′ components are allowed. The line strength S(J ′ , Ω′N ; J ′′ Ω′′ ) for a given
rotational line is given by:
S(J ′ , Ω′N ; J ′′ Ω′′ ) ∝




′
′′
′
′′
1
J 
J
1
J 
 J

µα 
 + µβ 

′
′
′′
′′
′
′
′′
′′
−ΩN (ΩN − Ω ) Ω−(ΩN + 1) (ΩN + 1 − Ω ) Ω

2
J′
1
J ′′ 

+µγ 
 ,
′
′
′′
′′
−(ΩN − 1) (ΩN − 1 − Ω ) Ω(2.7)

where µα , µβ , and µγ refer to the transition dipole matrix elements between the ground state andthe admixed excited states (of Ω′N , Ω′N +1, and Ω′N −1 character, correspondingly). Note that, since
the µα , µβ , µγ amplitudes are summed and then squared, interference effects are present. Thesematrix elements are allowed to vary in the contour fits. If the second and third terms are ignored,
the line strength expression reduces to the normal Hönl-London factor [94].
For the Π1/2 excited states, the ∆Ω = ±1, 0 transition selection rule requires the last term tobe zero. Between the two remaining transition dipole matrix elements, µα tends to dominate forall of the observed Π1/2 ← X 2 ∆3/2 bands. Similarly, µα tends to be the dominant dipole matrix
element for all of the Ω′ = 3/2 ← X 2 ∆3/2 bands except for two, {30.28} and {32.47}. Figure 2.5
compares the contour fits performed using the Hönl-London expressions versus Eq. (2.7) to describe
rotational line intensities for each of the anomalous bands. In both cases, the incorporation ofinterference effects in Eq. (2.7) gives rise to a better fit. In particular, the contour fits indicate an
admixture from a nearby Ω′ = 1/2 state (where µγ is dominant), which suggests that the observed

29
upper state is of nominal 2 Π3/2 character, the transition “brightness” from the ground state has
been lent to it from a nearby Π1/2 state. In fact, the rotational line strengths imply that at least
one of the two bands ({32.47}) is located very close to a Π1/2 ← X 2 ∆3/2 band, as seen in Fig. 2.4.
The observed admixture of electronic states is the reason for using Hund’s case (c) notation to
specify the Ω′ = 3/2 excited states.

2.5

Large isotope shifts
As shown in part (a) of Fig. 2.4, several bands were observed to have isotope shifts morenegative than -1.6 cm−1 , which would correspond to the upper state of the transition having
vibrational energy that exceeds the lower state vibrational energy by more than 3000 cm−1 . If weassume a typical upper-state vibrational spacing of ∼ 600 cm−1 , a 3000 cm−1 vibrational change
implied a change in vibrational quanta, ∆ν ∼ 5. Deriving bond lengths from observed rotational
constants, one calculates extremely small Franck-Condon factors for such transitions. This posesa mystery: how were we able to excite these transitions? One possible explanation could bethat interactions between potential curves, say an anticrossing of some sort, generate a few levels
described by anomalously large vibrational constants, as depicted in Fig. 2.6(a). An upper-statevibrational constant as large as 1000 cm−1 , for instance, could yield an acceptably large FranckCondon overlap for the corresponding ∆ν = 3 transition. But it seems unlikely there would be
multiple electronic states with such exotically large curvatures in their potential curves. Moreover,in Fig. 2.4, the x-axis spacing between some pairs of points that are clumped along the y-axis
suggests that at least some of the large-isotope-shift bands have relatively modest upper-statevibrational spacing, perhaps 450–600 cm−1 .
As an alternative hypothesis to the picture of transitions involving large changes in the number of vibrational quanta, the anomalous isotope shifts could arise from isotope-specific accidental
degeneracies between two mutually perturbing excited states, each of which have, in the absenceof perturbation, smaller isotope shifts (Fig. 2.6(b)). In this case, the perturbing state would not
only cause the 178 Hf19 F and 180 Hf19 F states to split apart from each other, but also cause all of30

Ions (arb. units)

Ions (arb. units)2−8|µ | = 1(a) α 2|µβ| = 02|µγ| = 0(b)(c)|µα|2 = 0.03|µβ|2 = 0.17|µγ|2 = 0.79

−6

−4

−2

|µα|2 = 1|µβ|2 = 0|µγ|2 = 0|µα|2 = 0.02(d)|µβ|2 = 0.16|µγ|2 = 0.82

0

2

4
−1

(First photon energy) − 30731.4 cm

−8

−6

−4

−2

0

2

4
−1

(First photon energy) − 32465.9 cm

Figure 2.5: Contour fits (red) to the Ω′ = 3/2 ← X 2 ∆3/2 {30.73} and {32.47} bands (data shownas connected black dots). In (a, c), the contour fits are constrained to use Hönl-London expressions
for the rotational line strengths, which are shown here to be inadequate for a good descriptionof the observed line intensities, especially for those in the Q branch. In (b, d), the contour fits
are allowed to take into account possible interference effects between parallel and perpendiculartransition moments. In both cases, µγ dominates over the other transition dipole matrix elements,
indicating that the nominal Ω′ = 3/2 upper states in both cases appear to possess an admixture
from nearby Ω′ = 1/2 states.

31
the other isotopologues to follow an irregular splitting that is not linear withp

1/(i) µ. Figure 2.7

displays the isotope splitting between the four most abundant isotopologues for several bands withlarge isotope shifts. The isotopologues are found to follow a linear energy spacing relative to theinverse square root of their reduced masses, which is what we expect in the absence of such an
isotopologue-specific perturbation and where the observed isotope shift is determined primarily byp
1/(i) µ vibrational energy shifts.

The high visibility of bands that had large isotope shifts could also be due to spin-orbit

interactions between vibrational levels that belong to different excited states, as shown in Fig. 2.6(c).
The observed excited state of a high vibrational quantum number, νd′ , could have been an initially“dark” electronic state that became observable by spin-orbit interaction with a “bright” electronic
state of much lower vibrational quantum number, νb′ . This would provide the latter with decent
Franck-Condon overlap with the lower state. Such a spin-orbit interaction would be proportional
to the vibrational overlap matrix element, hνd′ |νb′ i [48], which is estimated to be large only forνd′ ≈ νb′ ± 1 for all the observed excited states in HfF.
One plausible explanation for the large isotope shifts is that there may be a third state thatinduces an indirect interaction between the observed state and another “bright” state, where the“bright” state is of a significantly lower vibrational quantum number and has large Franck-Condon
overlap with the lower state (Fig. 2.6(d)). It is likely that there are other plausible explanations forthe observation of such anomalously large isotope shifts, and we invite the interested spectroscopist
to offer his or her ideas.

2.6

Intermediate states for OODR autoionization
Among the six Π1/2 ← X 2 ∆3/2 bands with 180 Tee′ in the range 31200–31900 cm−1 , two of

the bands ({32.22} and {32.32}) have been scanned at high resolution, using the (1+1′ ) REMPI
technique. Their distinct Λ-doubling constants, coupled with the close proximity of the electronicenergy levels, indicate that they must belong to electronically distinct states in order to exhibit suchsmall repulsion. Their dominant electronic configurations must differ by at least two spin-orbitals,

32

(a)

(c)
high n’dlow n’bbright(b)

176Hf19F

176Hf19F

dark

(d)

177Hf19F

177Hf19F
178Hf19F

high n’d178Hf19F

179Hf19F

179Hf19F

180Hf19F

y’

1

y’

180Hf19F

low n’b

Indirect
perturbation

2

Figure 2.6: Four hypotheses for the observation of large isotope shifts. (a) Avoided crossing ofpotential energy curves, giving rise to anomalously large vibrational spacings. (b) Isotope-specific′′accidental degeneracies between two mutuallyp perturbing excited states, ψ1 and ψ2 . In this picture,
the isotope splittings would not be linear in 1/(i) µ. (c) Local perturbation between a high-νd′ levelof a “dark” electronic state and a low-νb′ level of a “bright” electronic state. The higher νd′ level
becomes observable by borrowing brightness from the low-νb′ level, but it has the normal isotope
shift of a high-νd′ level. (d) Indirect coupling between the high-νd′ level and low-νb′ level.

33

3{ 30.73}

2

179

1

1

180
177

{ 32.91}−1

ν0 (cm )

180

177
178

0
3

2

178
179

1

(i)

ν0 −

{ 32.34}

177
178

2

(i)

ν0 −

180

−1

ν0 (cm )

3

0

180

q

0
6

179
180

{ 32.98}
4
178
179

2
180
0

1/(i) µ177q1/(i) µFigure 2.7: For the vibronic bands {30.73}, {32.34}, {32.91}, and {32.98}, the isotope shifts arefound to vary linearly with the inverse square root of the isotopologue reduced masses, whichsuggests that anomalously large isotope shifts are indeed due to a large ∆ν and not to isotopespecific perturbations.

34
e.g. sdδ(3 ∆1 )nℓλ versus s2 (1 Σ+ )n′ ℓ′ λ′ , where sdδ(3 ∆1 ) or s2 (1 Σ+ ) refers to the core configurations,and nℓλ or n′ ℓ′ λ′ refers to an additional electron in a more highly excited orbital. These two
configurationally distinct states could potentially be used as intermediate states to access different
states of HfF+ when performing OODR autoionization, which is relevant to our goal of preferential
population of the metastable 3 ∆1 state rather than X 1 Σ+ for the eEDM experiment. These two
vibronic states have indeed been observed to yield very different autoionization spectra, as shownin Fig. 2.8. We are in the process of characterizing the electronic states of the ions so produced.

Ions (arb. units)(a) {32.22}(b) {32.32}
−100

0
100
200
300
400
500
600
700
−1
Total excitation energy offset from ionization potential (cm )800

Figure 2.8: OODR autoionization spectra measured by tuning the first photon to access a particular excited rotational state (J ′ = 1/2(a)) using the vibronic bands (a) {32.22} and (b) {32.32}(ion signal inverted for clarity), then scanning the second photon to map out the spectrum of autoionizing Rydberg states accessible from that intermediate state. Each case gives a unique set of
autoionization resonances, suggesting that the ionic core of the autoionizing Rydberg state differs
between the two cases.

2.7

Summary
A plethora of HfF bands in the 30000–33000 cm−1 region have been observed using (1+1)REMPIand (1+1′ ) REMPI. We have characterized six Ω′ = 3/2 ← X 2 ∆3/2 and ten Π1/2 ← X 2 ∆3/2 vibronic bands. To sort out the spectra, we used the isotope shift for a given band to determine theelectronic energy, 180 Tee′ , for the upper electronic state. This method of grouping bands only works

for bands where the potential energy curves are fairly well-approximated by a harmonic potential. Two bands exhibit interference effects between parallel and perpendicular transition moments

35
through their rotational line strengths. Several bands with anomalously large isotope shifts had
intensities much larger than predicted based on the expected small Franck-Condon factors for transitions from the low-ν ′′ lower state. Among the six Π1/2 ← X 2 ∆3/2 bands with electronic energy
offsets crowded in the vicinity of 31300–31800 cm−1 , there are at least two electronically distinct
states. When such configurationally distinct states are used as intermediate states in the OODR
preparation of Rydberg states, these states provide access to at least two possible routes for creating
distinct HfF+ electronic states after autoionization decay, which will be important for the selective
formation of ionic HfF+ in the desired 3 ∆1 quantum state for the eEDM experiment.

Chapter 3
Autoionization for preparing HfF+ in a single rovibronic (1 Σ+ ) state [52]A high-precision search for the eEDM demands the preparation of as many HfF+ ions of asingle isotope as possible in a particular |J + , M + i rovibronic, Zeeman sublevel. Unwanted ionscreated in other states are co-trapped and can collide with the relevant ions, contributing to thedephasing of the latter species. The reduction in both the relevant sample number and coherencetime can doubly hurt the sensitivity of an eEDM experiment. Hence, the state preparation of HfF+
in a single rovibronic, Zeeman level is an important but non-trivial task.
The strategy we use to prepare HfF+ in a state-selective manner is the autoionization of
Rydberg HfF molecules excited from ground state HfF using the optical-optical double resonance(OODR) technique [48]. These autoionizing states lie above the lowest ionization threshold. Theirion-core is excited and decays after a short time, releasing energy to kick out the Rydberg electron.
Will the resultant state of the ion have some memory of the state of its parent Rydberg molecule?
In principle, the above question can be answered by building a model of autoionization basedon multichannel quantum defect theory (MQDT) [25, 37, 80, 31], like that performed for CaF[41]. This model calculates the quantum defect matrix elements µ(R, E) and their derivatives withrespect to the internuclear distance R and energy E, which can then be used to describe the Rydberg
energy spectrum, dynamics of autoionization and resultant ion states. However, constructing such aquantum defect model demands extensive knowledge of Rydberg levels to provide input parameters;such knowledge is presently lacking for HfF.
Alternatively, we tackle the question of Rydberg state – ion state branching ratios by experi-

37
mentally probing the post-autoionization states of HfF+ with laser-induced fluorescence (LIF). Ion
LIF has been reported before by other groups as a tool to examine the states of ions created fromresonance-enhanced multiphoton ionization (REMPI) [20, 27, 28, 90, 67] , electron-impact ionization [59] and ion-molecule collisions [32]. A slightly different but related form of state detectionis the grating-dispersed fluorescence obtained from highly-excited ions formed by photoionization
using synchrotron light sources [43, 68, 38, 17, 66]. In our experiment, the ions are formed from a
Rydberg band at 54 cm−1 above the lowest ionization threshold. The upper levels of this Rydberg
band are energetically allowed to decay only to the X 1 Σ+ (ν + = 0) vibronic ground state of HfF+ ,although the ions could be spread out over as many as ≈ 200 distinct |J + , M + i rotational-Zeeman
sublevels. The ion distribution over the various |J + , M + i states remain to be unveiled throughtheir LIF intensities.
To predict the ion population distributions, which are connected to the observed fluorescenceintensities, we present a simplified model of autoionization that assumes: 1. the Rydberg molecule
has the same electronic ion-core as its autoionization product, and 2. the Rydberg electron flies
off with the same angular momentum as it possessed when it was bound to the molecule, i. e. thedynamics of autoionization are radial only. The first assumption is based on the picture that
the Rydberg state undergoes vibrational autoionization as opposed to electronic autoionization;in vibrational autoionization, propensity rules tend to favor a νRyd = 1 → ν + = 0 decay process[48]. The second assumption means that unlike the quantum defect model, the simplified model
neglects the matrix elements of ∂µ/∂R that are off-diagonal in the Rydberg electron’s orbital
angular momentum l. We do not yet understand the HfF Rydberg spectrum sufficiently well, in
fact, to independently test these two assumptions. Instead, the severe lack of information obligates
us to propose an initial model that is as simple as possible. As will be seen, the model can be
adjusted to give a good account of the ion rotational distributions, and with no further adjustment
it does well predicting the orientation and M + populations of a particular J + level. That said, on
the basis of the present work alone, we cannot rule out electronic autoionization nor the presence of

38
angular dynamics in the autoionization process. The remaining sections of this chapter1 detail theexperimental methods, autoionization theory and results of our LIF studies on autoionized HfF,
with the primary goal toward maximizing ion creation in a desired single |J + , M + i state.

3.1

Experiment setup
Fig. 3.1 shows a schematic of the OODR-LIF experiment setup used to ionize a HfF molecularbeam and probe the resultant ionic states. The source chamber is the same as that described in
Section 2.1, while the OODR-LIF chamber replaces the TOFMS chamber. The two skimmers
responsible for collimating the molecular beam are also now replaced by skimmers of 3 mm orifice
diameter, separated by 12.5 cm. Three co-propagating lasers — two for OODR and one for LIF of
the ions — enter and exit the OODR-LIF chamber through Brewster-angled windows mounted on
15-cm long tubes, in which baffles are placed to reduce scattered light. The three lasers intersect
the molecular beam axis at 90◦ and the HfF+ ions produced are accelerated by an electric fieldof 0.3 V/cm through 5 cm to two microchannel plates (MCP) stacked in a chevron configuration.
The ion signal, after amplification by a transimpedance amplifier, is monitored on an oscilloscope.
Fluorescence photons are collected above and below the ion beam for 2 µs after the ions are excited.
The mirror on top collects most of the fluorescence photons and directs them to a parabolic mirror
below, which in turn focuses them onto a photomultiplier tube (PMT). To further reduce scattered
light counts, the photomultiplier tube is not gated on until 200 ns after the LIF laser fires. A
bandpass filter centered at 820 nm is also placed between the top collection mirror and the parabolic
mirror. The photon signals are amplified by a transimpedance amplifier, accumulated over at least
500 shots using a separate channel of the oscilloscope and counted individually using a peak-finding
algorithm.
All three lasers involved in addressing the energy levels in the OODR-LIF scheme, as depicted
in Fig. 3.2, are dye lasers. The first OODR laser pulse (309 nm, 1.5 µJ/pulse, 10 ns, 150 MHz
FWHM) is the output of a home-built two-stage Rhodamine 101 dye cell amplifier, frequency
1

Most of this chapter has already appeared in Reference [52].

39
doubled with a β-BBO crystal. The dye cell amplifier is seeded by a continuous-wave ring dye laser
operating with Rhodamine 610 Chloride dye and pumped by the second harmonic of a Nd:YAG
laser. The Nd:YAG second harmonic at 532 nm also pumps a dye laser operating with Pyridine 2,
the output of which is frequency-doubled with a KDP crystal to produce the second OODR laser
pulse (345–370 nm, 100–200 µJ/pulse, 10 ns, 0.1 cm−1 FWHM). The second laser pulse is delayedby 14 ns relative to the first laser. The LIF laser pulse (769 nm, 6–8 ns, 0.5 uJ/pulse, 100–200 MHz)is the output of a home-built two-stage LDS 798 dye cell amplifier, which is pumped by the second
harmonic of a Nd:YAG laser and seeded by an external cavity diode laser at 769 nm to address
the [13.0]1(ν ′ = 0) ← X 1 Σ+ (ν ′′ = 0) transition1 [16] in 180 Hf19 F+ . The LIF laser is delayedby 2 µs relative to the OODR lasers. Dichroic mirrors are used to overlap the three laser beams
spatially before they enter the vacuum chamber. The laser pulses are linearly polarized either
by the orientation of their frequency-doubling crystals or by passing through a polarizing beam
splitter. They can then be set to either left or right circular polarizations using quarter and half
waveplates for the appropriate wavelength ranges. Throughout the experiment, the frequenciesof the seed lasers for both the first OODR and LIF lasers are locked to a single rotational line
using a high-precision wavemeter that is regularly calibrated against the 87 Rb D2 transition. The
frequency of the second OODR laser is monitored by both the high-precision wavemeter and asecond wavemeter that is internally calibrated against Ne spectral lines.
To record OODR autoionization spectra, we fix the first OODR laser pulse on a single rotational line of a given parity of the [31.5]1/2 ← X 2 ∆3/2 transition2 [51] in the 180 Hf19 F isotope while
scanning the second laser pulse in frequency. We use circular dichroism techniques (i.e. we compare
the ion signal obtained when both lasers are polarized with the same helicity versus when polarizedwith opposite helicity) to identify transitions to various Rydberg rotational levels (denoted as J)
in the autoionization spectra [96, 65].
1“[13.0]1(ν ′ = 0)” refers to an excited state of vibrational quantum number ν ′ = 0, total angular momentum
projected on the body-fixed axis Ω = 1, and at 13,0xx cm−1 from the vibronic ground state of HfF+ .
2
Similarly, “[31.5]1/2” refers to an excited state of Ω = 1/2, and at 31,5xx cm−1 from the vibronic ground stateof HfF.

40
Rovibronic state detection of the HfF+ ion yield is accomplished by counting fluorescencephotons that are emitted down to the X 1 Σ+ (ν ′′ = 1) vibronic level [63, 4] when the ions are
excited by the LIF laser pulse. The frequency of the LIF laser is chopped every 100 shots between
being on-resonance and 500 MHz off-resonance of a rotational line. The number of fluorescencephotons detected when the horizontally-polarized LIF laser is tuned to an R(0), Q(1), Q(2), ... ,Q(5) transition is related to the rotational populations in the J + = 0, 1, 2, ..., 5 levels respectively.
Both OODR laser pulses are set to right circular polarizations. LIF detection is carried out when
the second OODR laser pulse is tuned to both on-resonance and ±0.35 cm−1 off-resonance ofan autoionizing line, so as to subtract out the contribution to the measured LIF intensities from
non-resonantly produced ions.
To determine the orientation of the ions formed in the J + = 1 rotational state, the LIF
laser is fixed on either the Q(1) or the R(1) transition. With both OODR lasers right circularly
polarized, we chop between having the LIF laser left and right circularly polarized and measure therespective fluorescence signals. Half waveplates and quarter waveplates are mounted on motorized
rotation stages to perform the polarization switching.
Ar (99%)+Sf6 (1%)

Ablation
laser

Q

Hf
Pulsedvalve

AblatedHf target

ac
b
d a
bc
d a
bc
d a
bc
d a
bc
d
bc
a
d a
bc
d a
bc
d a
bc
d
bc
a
d a
bc
d a
bc
d a
bc
d a
bc
d
bc
a
d a
bc
d a
bc
d a
bc
d
bc
a
d a
bc
d a
bc
d a
bc
d a
bc
d
bc
a
d a
bc
d a
bc
d a
bc
d
bc
a
d a
bc
d a
bc
d a
bc
d a
bc
d
bc
a
d a
bc
d a
bc
d a
bc
d

LIF Laser +1+1’ Ionization lasers

F

Skimmers

Hf+

F

MCP

PMT

Parabolic mirror

Figure 3.1: Schematic of the OODR-LIF apparatus. The molecular beam axis, the direction of
propagation of the three co-propagating lasers and the axis of fluorescence photon collection are
mutually perpendicular. From the ions, the fluorescence collection mirror on top subtends a polar
angle of δθ = 75◦ , whereas the parabolic mirror below subtends θ = −11.8◦ to 8.4◦ . A 820nmbandpass filter, placed between the top collection mirror and the parabolic mirror, is not shown.

41

OODR
Rydberg
W=3/2, J

W=1, v+’=0, J+’
(V)

(III)
(II)

2

LIF

P1/2, v’=0, J’(IV)

v+=1, J+’’
v+=0, J+

} 1S0+(I)
2

X D3/2, v”=0, J”

HfF

HfF+

Figure 3.2: Neutral HfF and HfF+ energy levels addressed in the OODR-LIF scheme. The quantum
numbers assigned to each rotational level follow those given in Section 3.3. The transitions marked
by roman numbers correspond to the following: I) first excitation photon in the OODR technique,II) second excitation photon in the OODR technique, III) autoionization, IV) laser-driven transitionin LIF, and V) fluorescence photons detected by the PMT.

42

3.2

Autoionizing states of hafnium fluoride
Transitions to different Rydberg rotational levels can be made by tuning the first OODR

laser pulse to access intermediate states of different J ′ and parity, as shown by the stacked plots in
Fig. 3.3a. The various rotational transitions driven by the first OODR laser pulse are labeled on
the top left corner of each subplot. Since the Ω-doublets of the X 2 ∆3/2 ground state in HfF cannot
be resolved by the first OODR laser, the parity of the Rydberg states can only be determined
up to an overall sign and is assigned as either ‘a’ or ‘b’ instead of as ‘e’ or ‘f’. The Rydberg
rotational levels are identified using the circular dichroism technique outlined in Section 3.1; forthe autoionization spectrum shown in Fig. 3.3a, both OODR lasers are chosen to be right circularly
polarized to enhance the autoionization line intensity from higher J states. The level spacings arise
from half-integer pattern-forming quantum numbers, which indicate that the Rydberg electron
is core-penetrating, i.e. the inner lobe of its wavefunction lies inside the molecular ion-core [40].
Since no transition to the J = 1/2 level is observed, the Rydberg vibronic band is inferred to have
Ω = 3/2. The Ω-doublets of the Rydberg vibronic band have no observable energy splitting, even up
to J = 11/2. The Rydberg rotational energies are fit to the polynomial E(J) = T0 + BRyd J(J + 1),
yielding a rotational constant of BRyd = 0.2911(6) cm−1 . The J = 7/2 and 11/2 levels are foundto be perturbed by as much as -0.16(2) cm−1 and +0.27(3) cm−1 from the expected energy levelsof a rigid rotor.
The Rydberg vibronic band characterized at 54 cm−1 above the lowest ionization threshold(59462(2) cm−1 ) is part of a broader scan of the autoionization spectrum, shown in Fig. 3.3b. In
contrast to the anomalously clean series of rotational lines in Fig. 3.3a, the HfF autoionization
spectrum is generally cluttered. Although the pulse energy of the second OODR laser is reduced
to avoid saturating the transitions to Rydberg states, the autoionization spectrum contains manybroad features, the narrowest of which, at 0.3 cm−1 , is three times broader than the linewidthof the second OODR laser. This broadening cannot be attributed to either lifetime or hyperfine
structure. The clutter of features makes it impossible for us to identify a clean Rydberg series of43lines leading to ionization thresholds 3 .
The identification of various Rydberg series and their underlying Rydberg electron character
could potentially lead to predictions of ion rovibronic distributions. Alternatively, we can measure
the distributions of the ions formed and work backwards to elucidate the character of the Rydberg
electron. Toward this end, we developed a simplified model of autoionization, presented in thefollowing section.

3.3

TheoryIn this simplified model of autoionization, the Rydberg molecule is treated as a Rydberg

electron attached to a 1 Σ+ ion-core at relatively short distances. The good quantum numbers of
the resonant Rydberg state include the total angular momentum of the molecule J, its projection
on the molecular z-axis Ω (approximately), its projection on the laboratory z-axis MJ , and theparity of the molecule. The quantization (ẑ) axis in the laboratory is provided by the directionof laser propagation. The anisotropic interaction between the outermost electron and the ion-core
couples the orbital angular momentum l and total angular momentum j of the Rydberg electron.
Neglecting the vibrational part, we write the short-range Rydberg states as a superposition of basis
states having definite values of l and j:Ψres =X|Ω|P

Alj ψlj

,

(3.1)

lj

where Alj is the probability amplitude of the corresponding {l, j} partial wave, and where"
X j|Ω||Ω|P1
ψlj = √2
R (J |Ω| MJ )ClΩ;sσ YlΩ χsσΩσ− (−1)j+J−l+P R (J − |Ω| MJ )

X
Ωσ

j−|Ω|
ClΩ;sσ YlΩ χsσ

#

.

(3.2)

In Eq. (3.2), C, YlΩ , and χsσ denote a Clebsch-Gordan coefficient, spherical harmonic, and spinorJ
wavefunction, respectively. R (JΩMJ ) is related to the Wigner rotation matrix DM, which is aJΩ3

The lowest and excited HfF ionization thresholds have been identified using pulsed field ionization – zero electron
kinetic energy (PFI-ZEKE) photoelectron spectroscopy[4]44(a) R(7/2)

9/2

Ions

R(5/2)

7/2

R(3/2)

Q(3/2)

5/2

5/2

*

3/2

53

55

a
b
57

59

61

63

65

*

Ions

49 51
(b)
P(3/2)

9/2

7/2

3/2

P(3/2)

11/2

−40

−20

0

20

40

60

Total excitation energy offset fromionization potential (cm−1)

Figure 3.3: (a) Stacked plots of OODR autoionization spectra, measured by scanning the frequencyof the second photon while holding the first photon fixed on different ground-intermediate transitions (denoted on the left of the figure as ‘P(3/2)’, etc.) to access different intermediate rotational
states. The identified Rydberg rotational energy levels are marked by solid black lines with theircorresponding assignments. The autoionization spectra shown as blue dots (red triangles) belong
to the same parity ‘a’ (‘b’). The ionization energy given by the x-axis is referenced to the groundrovibronic level in neutral HfF [1] and is offset from the ionization potential, 59462(2) cm−1 . (b)A broader scan of OODR ionization spectra is conducted in an electric field of ≈ 25 V/cm, which
explains the appearance of peaks in ion creation at ∼ 30 cm−1 below the ionization potential of
HfF. The peak marked by an asterisk is the same peak as that in (a).

45function of the Euler angles {α, β, γ} ,R (JΩMJ ) =r∗
2J + 1  J
.
D
(αβγ)
M
Ω
J
8π 2

(3.3)

The parity of the molecule is given by (−1)P .
After autoionization, the distance between the emitted electron and the ion-core is large.
This long-range (electron +HfF+ ) system is described by the total ionic angular momentum J + ,its projection M + on the laboratory z-axis, and its projection Ω+ on the body-fixed z-axis. Here,Ω+ = 0 since the ion is in a 1 Σ+ state. Because the short-range states have a definite total angularmomentum J and projection on the laboratory z-axis MJ , we also want to construct the long-range
states with definite J and MJ . We assume that the Rydberg electron flies off with the same {l, j}angular momenta it possessed when bound to the molecule, i.e. there are no angular dynamics inautoionization. The {l, j} partial waves of the system after autoionization can then be written as+

φJlj =

X

M + mj

 X jmj
+
+
+
J
=
0,
M
×
CJJM
Clλ;sms Ylλ χsms .
+ M + ;jm R J , Ω
j

(3.4)

λms

Eqs. (3.2) and (3.4) can be related by a rotational frame transformation,|Ω|Pψlj = (−1)j+|Ω|

X

J +0
Cj−|Ω|,J|Ω|

J+

q

+

+

1 + (−1)l+J +P φJlj .

(3.5)

Hence, after autoionization, the probability for a Rydberg state with quantum numbers J and MJ
to produce an ion in the |J + , M + i state is
J
PJJ,M+ ,M + =

P
lj

i
i2 h
i2 h
h +
l+J + +P
J 0
J
.
1
+
(−1)
CJJM
|Alj |2 Cj−|Ω|,J|Ω|+ M + ,jmj

(3.6)

In the experiment determining the ions’ rotational distribution, the resonant Rydberg state isprepared by two right circularly polarized laser pulses. The OODR excitation steps are denoted as(X 2 ∆3/2 )J ′′ → (Π1/2 )J ′ → (Rydberg Ω = 3/2) J. The molecules are assumed to reside initially ina random distribution of MJ′′ sub-levels. The relative probability for a resonant Rydberg molecule
to be prepared in a |J, MJ i level is then given by
′

JMJ
J
J −1
= CJJ′′M
PM
MJ −2;11 CJ ′ MJ −1;11
J

2

,

(3.7)

46
where saturation effects are assumed negligible. The final (unnormalized) rotational distributionof the ions is obtained by combining Eq. (3.6) with Eq. (3.7):
PJJ+ M + =X

JPMP MJ .
J J +M +

(3.8)

MJ

The rotational distribution given by Eq. (3.8), however, cannot be compared against theexperiment directly. In the experiment, LIF signals for the different J + states are measured.
′

The ions are excited by an x-polarized laser tuned to the rotational transition J + → J + and′′subsequently emit photons as they decay radiatively to some lower state J + . The x-polarizedlaser can be described by a linear combination of two spherical harmonics √12 (Y1−1 − Y11 ). Since
the photomultiplier tube collects photons of both Y1−1 and Y11 polarizations emitted in almost all
directions, we can add the probabilities corresponding to each spherical harmonic incoherently. For
a given spherical harmonic Y1q , the relative signal strength has been adapted as a generalization of
Eq. (23) in Ref. [34]:(q)

IJ + M + ,J +′′
2J + + 1 2J + + 1
2
2 

+
+′
+
+′
J
1
J
J
1
J
 


× 
 

′
′
′
−M + −q M +−Ω+ Ω+ − Ω+ Ω+

=

′

×

′′

+ +1
JX

+
J
X

J +′′ =|J +′ −1| M + =−J +




× 

′′

′
J+

−Ω

+′

′′

′′
J+

1
Ω

+′

−Ω




′
′′
2J + + 1 2J + + 1

+′′

Ω

+′′

2 
 
 

′
J+

−M

+′

1
−q ′

′′
J+

M

+′′

2


 .

(3.9)

The first two lines describe the laser excitation step and the last two lines describe the spontaneousemission step of the LIF process. The summation in the last two lines gives unity. Hence, for a47given |J + , M + i state, the relative LIF signal strength for an x-polarized LIF excitation is given by
IJ + M + ,J +′××
1  (+1)(−1)
IJ + M + ,J +′ + IJ + M + ,J +′
2


1
′
=
2J + + 1 2J + + 1
2
2

′
+
+
1
J 
 J


′
′
+
+
+
+
Ω
−Ω
Ω −Ω

2 
2 
′
′
+
1 J+  
1J+  J +
 J

 
 +

.
′
′
+
+
+
+
−M
1 M
−M
−1 M
=

(3.10)

Finally, the relative LIF signal strength, to be compared against the measured LIF intensities that
trace over the M + levels, is given by
IJ + ,J +′ =1 X J
P + + I + + +′ ,N + J M J M ,J

(3.11)

M

where N is a normalization factor chosen such thatP

{J + ,J +′ }IJ + ,J +′ = 1. We use Eq. (3.11) to fit

IJ + ,J +′ to the measured LIF signal and determine the values of |Alj |2 . The effects of excited state′(J + ) alignment and orientation on the photon collection efficiency were evaluated and found to bevery small.
When probing the orientation of the ions, the LIF excitation laser is either right or left
circularly polarized. The LIF signals for these cases are then given byγR =X

PJJ+ M + IJ + M + ,J +′ ,(1)

(3.12a)(−1)(3.12b)

M+

γL =

X

PJJ+ M + IJ + M + ,J +′ .

M+

3.4

Rotational distributions and parity propensities in autoionization decay
The fluorescence intensities, measured by exciting ions formed in various rotational states of

the X 1 Σ+ , ν + = 0 vibronic ground state after autoionization, are given in Fig. 3.4a. We focus on
the ions produced from both parities of the J = 3/2 and 5/2 rotational Rydberg levels. Although
the Rydberg molecules at 54 cm−1 above ionization threshold are energetically allowed to decay into

48
many rotational levels of HfF+ , they are observed to autoionize into only a few rotational levels.
The Rydberg molecules of a given parity are further observed to decay into ion rotational levels of
the same parity, i.e. molecules from the ‘a’ (‘b’) Rydberg state primarily form ions in the odd (even)rotational states, as shown on the left (right) side of Fig. 3.4a. Both the rotational propensity andparity propensity observations have also been reported for near-homonuclear molecular ions like N+
2and NO+ created from REMPI [27, 90, 61], and are accounted for in a theory paper by Xie and Zare[91]. For a polar molecule like CaF+ , however, the parity propensity rule tends not to hold due toextensive l-mixing for the Rydberg electron. For the HfF vibronic band reported here, the parity
propensity observation indicates the release of a Rydberg electron with l of predominantly one
parity. On the other hand, the non-negligible formation of ions in rotational states of both parities
implies that the Rydberg electron was ejected with a superposition of orbital angular momenta.
We use Eq. (3.11) from the simplified autoionization model to generate fluorescence intensities for each allowed {l, j} and fit them against the LIF data to obtain the angular momentum
composition of the Rydberg electron. We note that since the overall parity of the Rydberg statescannot be determined a priori, there are two possible sets of Alj to which the data could have fit.
However, the fits only converged for one of the two cases, strongly suggesting that the Rydberg
states denoted by ‘a’ (‘b’) should be assigned the parity P = +1(−1) in Eq. (3.1). In this case, thefit results gave 67.5(3.7)% p3/2 , 9.8(4.5)% d3/2 and 22.7(5.3)% d5/2 character to the Rydberg electron, where the numbers in parenthesis indicate the 1σ-error. In accordance with the half-integer
quantum number progression of the Rydberg rotational states, the Rydberg electron is found to be
in primarily a core-penetrating state. The mixed {l, j} character of the HfF Rydberg state has also
been reported for CaF Rydberg molecules [41]. We acknowledge that in contrast to the presented
model, other groups have reported significant angular dynamics in autoionization, which may be
accounted for within the framework of MQDT: for example, the Rydberg electron may have onlya single set of {l, j} when bound to the molecule, but flies off with multiple {l, j} [61], leading to
the formation of ions in rotational states of both parities. Since the {l, j} composition of the HfF
Rydberg state is not known a priori, we cannot claim the validity of our model over others.

49
From the fits to the LIF intensities, the population distribution of HfF+ ions in the various
rotational states can be obtained (see Fig. 3.4b). There can be as many as 60% of the ions createdin a single rovibronic state (highlighted as black solid bar plots), which is significant for the state
selective creation of HfF+ for future experiments.

3.5

Preservation of orientation in autoionization decay
Certain experiments demand not only the creation of molecular ions in a particular rovibronic

state, but in a single Zeeman level of that state. To this end, we experimentally determine theorientation of HfF+ formed in the J + = 1, ν + = 0, X 1 Σ+ state from the Rydberg levels J = 3/2(a)and J = 5/2(a) prepared using two right circularly polarized OODR photons. The ‘a’ parity states
are chosen to maximize the ion signal, given the parity propensity rule observed in the previous
section. Unlike when measuring the ion rotational populations, the orientation was only determined
for when the OODR lasers are tuned to the resonance of an autoionizing line, as the non-resonant
ions were found to contribute to only ≈ 20% of the population in J + = 1.The orientation is related
to the contrast ratio C for the fluorescence signal (γR , γL ) measured when chopping between rightand left circular polarizations for the LIF laser, where C is defined as
C≡γR − γL.
γR + γL(3.13)

The contrast ratio is a convenient quantity immune to drifts in ion production. As a systematic
check of our polarizations, we measured the contrast ratio when both OODR laser pulses are left
circularly polarized and found C to be of the same magnitude but opposite sign as when both lasers
were right circularly polarized, as expected.
The contrast ratios for the Q(1) and R(1) transitions are related to the orientation O0 andalignment A0 of the ions through the following [26]:C Q(1) =3(1 + G1 )O0,
A0 − 2(1 + G2 )(3.14a)C R(1) =15(1 + G3 )O0,
A0 + 10(1 + G4 )(3.14b)

50

Signal photons per shot(a)

5/2 (a)

0.2

0.2

0.1

0.1

0

0

0.4
3/2 (a)

0.2

0.2

0.1

0

0
0 1 2 3 4 5(b) 0.6
Normalized ion population

5/2 (b)0.4
0.2

5/2 (b)

0.2

0
0.6

0 1 2 3 4 5

5/2 (a) 0.6
0.4

x3/2 (b)0x
3/2 (a)0.4

0.4

3/2 (b)

0.2

0.2

0

0
0 1 2 3 4 5

0 1 2 3 4 5+ 1

N+ (1Σ0)N ( Σ0)Figure 3.4: (a) The Rydberg molecules, labeled by J and parity on the top right corner, areobserved to autoionize into only a few ion rotational levels. These rotational distributions areprobed by measuring the number of LIF photons, as shown in blue/red with error bars. In one
case (J + = 0 ← J = 5/2 (b)), the measured LIF intensity appears negative, which is a statisticalartifact of the multiple signal subtractions performed to account for scattered light photons andthe rotational distribution of background ions. The narrower bar plots are theory fits to the data.
(b) The calculated rotational distribution of ions is obtained based on the fits to the rotational line
intensities above. The creation of ∼ 60% of the ions in a single rotational level, as highlighted by
the solid black bars, can be a significant advantage for future experiments. The ions formed in the
J + = 1 state, marked by crosses above the bar plots, have their M + distributions further examined(see Fig. 3.5).

51
where {Gi } . 0.05 are correction factors that account for the anisotropy of the fluorescence collection setup (depicted in Fig. 3.1). The orientation and alignment parameters are in turn related to
the M + populations, which are displayed as plots with error bars in Fig. 3.5. The narrower bar
plots show the contrast ratios and M + -level distributions predicted from Eq. (3.12) of Section 3.3,
using the same Rydberg electron composition of {l, j} inferred from the rotational distributions.
The agreement between theory and experiment is good for the M + = 1 population but only fair
for the M + = 0, −1 populations, part of which may be attributed to the oversimplification of themodel’s assumptions. We note that of the decay into a single rovibronic state, the population in asingle Zeeman level may be as high as 54(7)% (from J = 3/2(a)) or even 73(6)% (from J = 5/2(a)).
In particular, the former number, combined with the formation of 60% of the ions in that samerovibronic state, means that as many as 30% of the HfF+ ions created from a certain autoionizing
resonance can be in a single |J + , M + i level.
Different rotational levels can have different maximal (minimal) values for their orientation,
given by O0max (= −O0min ) = 1/(J + 1). Therefore, instead of comparing the orientation parameterof the Rydberg molecule to that of the autoionized product, we compare the fractional orientation
O0′ :
O0′ =

O0 − O0min.
O0max − O0min(3.15)

O0′ is 1 (0) when only the |M + = +J + i (|M + = −J + i) states are populated and 0.5 when there is noorientation. From the values reported in Table 3.1, we find that the autoionization of HfF Rydberg
molecules to the J + = 1, ν + = 0, X 1 Σ+ rovibronic state preserves orientation qualitatively, whichbodes well for the creation of HfF+ predominantly in a single Zeeman, rovibronic level for otherexperiments.

3.6

Summary
We have spectroscopically characterized a vibronic band of the autoionization spectrum in

HfF at 54 cm−1 above the lowest ionization threshold. We directly probe the decay of its Rydberg

52

m+ populations

Contrast

JRyd
0.5

1

0

0.5

−0.5

0

5/2
(a)

1

0.2

3/2
(a)

0

0.5

−0.2

0
Q(1)

R(1)

−1

0

1

Figure 3.5: The Rydberg molecules in (top) J = 5/2(a) and (bottom) J = 3/2(a), prepared using
two right circularly polarized photons in OODR, are observed to decay into the ion rotational level
J + = 1 with a certain orientation. The ions’ orientation, related to the M + population distribution(right), is inferred from measurements of contrast ratios (left) for the Q(1) and R(1) LIF transition.
The narrower bar plots are the theory predictions for the M + populations.

Table 3.1: Fractional orientation O0′ of Rydberg HfF molecules in a given rotational level J andof the ions formed in J + = 1 after autoionization. The HfF orientation is calculated from thepolarizations of the OODR lasers; the HfF+ orientation is predicted from the simplified model of
autoionization described in the text; the HfF+ (measured) column refers to values inferred from
LIF polarization contrast ratios in Fig. 3.5.
J
3/2 (a)5/2 (a)Fractional orientation
Rydberg HfF
HfF+
HfF+
(calculated) (predicted) (measured)
0.835
0.633
0.645(62)
0.865
0.867
0.730(86)53
states (J = 3/2, 5/2) into various rotational states of the X 1 Σ+ , ν + = 0 vibronic ground state of
HfF+ by performing laser-induced fluorescence on the ions. The measured fluorescence intensities
are fit using a simplified model of autoionization that assumes no angular dynamics and that the
Rydberg state has the same electronic ion-core as its autoionized state. The fit parameters imply
that the Rydberg electron has dominant p3/2 character with some mixing from the d orbitals. Using
the same Rydberg electron character, the model predicts qualitative preservation of orientation
when the Rydberg molecule autoionizes to the J + = 1, ν + = 0, X 1 Σ+ state, which was corroborated
by fluorescence intensity measurements carried out after excitation by a circularly polarized laser.
Thanks to a combination of rotational propensity, parity propensity and preservation of orientation
during autoionization, we find that we can create as many as 30% of the HfF+ ions in a single
Zeeman level of a rovibronic state. Having an initial population of 30% of the ions in a single|J + , M + i level could prove to be very advantageous for future experiments such as the eEDM
search.
We note that although this work has concentrated on one vibronic band of a core-penetrating
Rydberg state, there is a body of core-nonpenetrating states in HfF that has yet to be uncovered
with experiment. Core-nonpenetrating states have almost pure l character. With l ≥ 2 for HfF,
the Rydberg electron hardly exerts a torque on the ion core rotational states when ejected, whichmeans that the resultant ion rotational states are likely to follow that of the Rydberg molecules
more closely. [42] This lends core-nonpenetrating Rydberg states even more promise for populating
ions of a desired |J + , M + i level with high efficiency.

Chapter 4
Ion traps

The aspect that best distinguishes the JILA eEDM experiment from the other eEDM efforts isthe fact that we work with molecular ions. As mentioned in the Introduction, molecular ions can betrapped easily with electric fields, whereas the trapping of neutral molecules is difficult. Trappedmolecular ions offer a potentially long coherence time, which the eEDM statistical sensitivity is
proportional to. Ions can be trapped using a Paul trap or a Penning trap, and the JILA eEDM
experiment employs the former. In this chapter, we review the basics of a linear Paul trap, describe
our own design of a linear Paul trap, and demonstrate several techniques used to characterize anddiagnose the ions’ in-trap behavior.

4.1

Linear Paul trap basics

4.1.1

A simple picture for the quadrupole trap

The conventional linear Paul trap consists of four radial (x̂, ŷ) electrodes and two axial end
cap (ẑ) electrodes (Fig. 4.1a). To confine the ions along the axial direction, one can apply a DC
voltage to the end cap electrodes Vec , such that the potential between the electrodes is describedby Φ1 (x, y, z):
x2 + y 2
1 ∂ 2 Φ12z−
2 ∂z 22
2
x + y22= k1 Vec z −,2

Φ1 (x, y, z) =

(4.1)

55
where k1 is a geometrical term related to the end cap electrode voltages giving rise to a second
derivative of the potential ∂ 2 Φ1 /∂z 2 . The deconfining potential along the radial direction (−(x2 +y 2 )/2) comes from Φ1 having to satisfy Laplace’s equation ∇2 Φ = 0. To confine the ions in theradial directions, one can apply an additional radiofrequency (RF) voltage to the radial electrodes,
creating a time-varying quadrupole potential Φ2 (x, y, t):1 ∂ 2 Φ2 2
x − y 2 cos(ω rf t)2
2 ∂x
= k2 Vrf x2 − y 2 cos(ω rf t) ,

Φ2 (x, y, t) =(4.2)

where k2 is again a geometrical factor relating the radial electrode voltages to the second derivativeof Φ2 . The total ion trap potential is given by Φ = Φ1 + Φ2 .
At any one point in time, Eq. (4.2) describes the radial potential as a saddle, i.e. it isconfining along one direction but deconfining along its perpendicular direction. Averaging over theions’ trajectory for 1 RF cycle, however, the radial potential becomes a harmonic pseudopotential
well in which ions can be trapped, as depicted in Fig. 4.1b. For simplicity, Fig. 4.1b considers
only the ion behavior along the x̂ direction. Initially, the electric field (of direction and magnitude
shown by the arrows) points outwards from x = 0 and displaces an ion from x0 to x1 (> x0 ), where
the magnitude of the electric field at x1 is larger than that at x0 . Half a RF cycle later, the electricfield switches direction and the ion moves back to x2 , where x2 < x0 since |E(x1 )| > |E(x0 )|.
Another half-cycle later, the ion is at x3 , where x3 < x1 since |E(x2 )| > |E(x1 )|. Continuing suchanalysis, one can see how the ion eventually oscillates back and forth through the origin as if it isin a harmonic potential well (i.e. secular motion), while exhibiting some “jerky motion” at a small
amplitude and at the radio frequency ωrf (i.e. micromotion).

4.1.2

Pseudopotential

To derive an expression for a 1-dimensional harmonic pseudopotential ψ in which a trapped
ion moves, we start with the force exerted on the ion of mass m and charge e:mẍ = eE0 (x) cos(ω rf t) = eE(x) ,where E0 (x) = −2k2 Vrf x .

(4.3)

56

(a)

y
x
z

-Vrf cos(wrft)

Vrf cos(wrft)(b)x0

wrft=0x1
wrft=px2

wrft=2px3
wrft=3px4

wrft=4p

e(x0)
e(x1)
e(x2)
e(x3)
e(x4)

x=0

(c)
a

q

Figure 4.1: (a) Linear Paul trap with the depicted electrodes providing radial (x̂, ŷ) confinement(adapted from [29]). The axially confining (ẑ) potential and axial electrodes are not shown. (b)A simple picture for the motion of an ion in a linear Paul trap. The arrows depict electric fields
along the x̂ axis of a linear Paul trap, oscillating at frequency ωrf . An ion (shown as the blackdot) starting at some initial position is subject to a force whose direction (along x̂) switches sign
every half RF cycle, causing the ion to exhibit micromotion whose amplitude is larger when theion is farther from the trap center. Overall, there is a net pushing of the ion towards the trap
center whenever the ion is displaced, hence the ion behaves like a harmonic oscillator with added
micromotion. (c) Stability diagram for the linear Paul trap with axial confinement, expressed interms of the trap parameters a and q, which are proportional to the axial end cap electrode voltage
Vec and RF voltage VRF , respectively. For sets of {a, q} within the gray shaded region, the ionscan be stably trapped.

57
Using the simple picture given in Section 4.1.1, we assume that the ion motion can be separated
into its secular motion X̄ and a fast but small amplitude micromotion δ that occurs at the drving
RF frequency ωrf :x = X̄ + δ, δ = A cos(ω rf t) ,(4.4)

¨ . To figure out the amplitude of micromotion A, we substitute the above
where X̄ ≫ δ, δ̈ ≫ X̄
¨ and δ are subsequently neglected because the secular
expression for x and δ into Eq. (4.3). X̄
motion is negligible on the time scale of the micromotion and the micromotion amplitude is too
small.
¨m X̄ + δ̈= eE0 (X̄ + δ) cos(ω rf t)

2
A cos(ωrf t) = eE0 (X̄) cos(ωrf t)
−mωrf

A = −
⇒δ = −

eE0 (X̄)2mωrf
eE0 (X̄)
2 cos(ωrf t) .
mωrf

(4.5)

Eq. (4.5) shows that the amplitude of the micromotion increases as the ions move farther from thetrap center.
The pseudopotential D̄ is related to the force exerted on the ion, averaged over one micro~ D̄. Performing a Taylor expansion of F̄ /e about the secular position X̄
motion cycle F̄ : F̄ /e = −∇and then averaging over a cycle of the micromotion:



1
∂F
|
F (x = X̄) +x − X̄
e∂x x=X̄
micromotion t


∂E
|
·δ
=
E(x = X̄) +∂x x=X̄
t
*
!+
(
E
(
X̄)
eE
(
X̄)
(
0
0
(( t) +
E0(
(X̄)
cos(ω
=
cos2 (ωrf t) · −
((
t
rf
(
2
mωrf
X̄

1
F̄ (X̄) =e(4.6)

In the last line, we made use of the fact that E0 (x) is linear in x, so that ∂E∂x = E/x. Then,~ D̄(X̄) = −−∇⇒ D̄(X̄) =eE0 (X̄)22mωrf

eE0 (X̄)2
2 .
4mωrf

(4.7)

58
Incidentally, the kinetic energy of the micromotion δ averaged over 1 RF cycle is also related toD̄(X̄):
hUδ i =
=

1
2
mωrf
δ2
2
1 eE 0 (X̄)22
4 mωrf= eD̄(X̄) .

4.1.3

(4.8)

Mathieu equations

More generally, the motion of an ion in an rf trapping potential is described by Mathieu
equations. Here we derive the Mathieu equations for an ion of mass m and charge e in the ion trap
described in Section 4.1.1, with the DC and radial RF potentials given by Eqs. (4.1) and (4.2),
respectively.
We start with the expressions for the electric fields in all 3 directions:−→→−
Erf = − ∇Φ2 = −2k2 Vrf (xx̂ − y ŷ) cos(ωrf t) ,(4.9a)−→→−
Ez = − ∇Φ1 = k1 Vec (−2zẑ + xx̂ + y ŷ) ,(4.9b)−→−→ −→E = Erf + Ez .

(4.9c)→−→−→
r = F = e E , we getUsing Newton’s second law m−̈
 


ẍ
(−2k2 Vrf cos(ωrf t) + k1 Vec )x
 

e 
 


ÿ  =
(+2k2 Vrf cos(ωrf t) + k1 Vec )y  .
  m z̈−2k1 Vec z(4.10)

We now make the substitutions:
τ
dx
dτ
d2 x
dτ 2

= ωrf t/2 ,
=
=

dx 2
,
dt ωrf 
d dx 24 d dx
4= 2= 2 ẍ ,dτ dt ωrf
ωrf dt dt
ωrf(4.11a)(4.11b)(4.11c)

59
which then give rise toed2 x+ (−4k1 Vec + 2 · 4k2 Vrf cos(2τ ))2 x = 0dτ 2mωrf

(4.12)d2 ye+ (−4k1 Vec − 2 · 4k2 Vrf cos(2τ ))2 y = 02dτmωrf

(4.13)

d2 z
e+ 8k1 Vec
2 z = 0.
2dτmωrf

(4.14)

1 Vec eNow, let a ≡ − 4kmω2 , q ≡

rf

4k 2 Vrf e
mω 2
rf



. Then, where r̈τ now refers to d2 r/dτ 2 ,







 

ẍτ  (a + 2q cos(2τ ))x 0
  
  
  
  
 ÿτ  + (a − 2q cos(2τ ))y  = 0 .
  
  
  
  
z̈τ
(−2a)z0(4.15)

Fig. 4.1c shows the stability diagram for the Mathieu equations. For certain values of {a, q}(depicted as the gray regions), the ion motion is stable and the ion remains trapped. For other setsof {a, q} (depicted as the white regions), the ion follows an unstable trajectory and is ejected fromthe trap.
Where a is small compared to q and where q 2 ≪ 1, we can rederive the pseudopotential interms of a and q by plugging Eq. (4.4) into Eq. (4.15) [29]:¨ + δ̈
X̄= −(a + 2q cos(2τ ))(X̄ + δ)

⇒δ =

q X̄
cos(2τ ) ,2(4.16)

which is the same expression as that given in Eq. (4.5). Plugging Eq. (4.16) into the first line of
Eq. (4.15) again to solve for X̄ and averaging over one micromotion cycle, we get an equation of
motion describing the secular motion:
D E
¨
X̄

τ




q X̄
= − (a + 2q cos(2τ )) X̄ +cos(2τ )
2
τ
+
*



q
X̄


2
2
 )−
cos(2τ ) − q X̄ cos (2τ )=−aX̄ − 2qX̄cos(2τ

2
τ


q2
= − a+
X̄ .
2(4.17)

60
Recalling that τ = ωrf t/2, we can see that the ion’s pseudopotential in the radial and axial directions
are D̄r = mωr2 r 2 /2 and D̄z = mωz2 z 2 /2, where
ωr =
ωz =

4.1.4

r
ωrf q 2
+a
2
2
ωrf √
−2a .
2

(r = x, y) ,(4.18a)(4.18b)Multiple ions

So far, the ion motion described applies very well to that of a single trapped ion. Whenmultiple ions are trapped, the potential felt by any given ion is modified due to space charge
repulsion by other ions. The maximum ion density is set by the confining pseudopotential D̄ being
as strong as the deconfining potential from the space charge repulsion φi [29]:−∇2 φi = ∇2 D̄ =
⇒

ρmax
ǫ0

ρmax
ǫ0


= ∇2 D̄x + D̄y + D̄z


1
2
2
= 2 mωr + mωz
2

 2
2
ωrf q
q2
= m
+a+
+ a − 2a
4
2
2
2
ωrf
= m q2 .
4(4.19)For our typical trap parameters, q = 0.59 and ωrf = (2π)50 kHz, so the maximum number of ionsthat can be confined in a spherical cloud of radius r2σ = 3 mm isρmax
Nmax = 2
e



4 3
πr
3 2σ



= 1.1 × 105 .

(4.20)

Another useful estimate is the following expression for the mean field space-charge repulsion
energy Umf of a cloud of Nions ions confined in a sphere of radius r [45, 83]:
Umf
Nions e2=
≈ 3K ×kB
4πǫ0 rkB



Nions
1000



r −1
.
0.5 cm

(4.21)

Where Umf is significant compared to the temperature T of trapped ions, instabilities and heating
are more likely to occur.

61
4.1.5

Rotating field

The application of a rotating bias electric field E~rot on top of the RF and DC voltages inthe {x̂, ŷ} plane is a novel feature in the operation of ion traps. The rotating bias field serves topolarize the HfF+ molecule and to provide a quantization axis for the eEDM experiment. If it were
not rotating, the bias electric field would simply eject the ions out of the trap. So, E~rot is kept
rotating at a frequency slow enough for the molecular axis to track but fast enough so that the ionsstay trapped as the radius of rotation remains small compared to the trap extent:~rrot = −eE~rot2 .
mωrot(4.22)

This circular micromotion ~rrot is superimposed on top of the trap RF micromotion and secularmotion. In contrast to the RF micromotion, ~rrot is not a function of secular displacement. To avoid
resonantly driving and heating the ions with the rotating bias field, care is taken to choose therotating field frequency to be incommensurate with respect to ωrf . The kinetic energy of the ions’circular micromotion, averaged over a rotation cycle, is much higher than the other energy scales
in the ion trap:
Urot =

2e2 Erot
2 .
2mωrot(4.23)

Table 4.1 lists the typical frequencies, electric fields, length scales and kinetic energies encounteredby the ions’ secular motion, trap RF micromotion and rotating circular micromotion.
Table 4.1: Typical frequencies, length scales and kinetic energies for the ions’ secular motion, trap
RF micromotion and circular micromotion due to Erot .
MotionSecular motion
Trap RF micromotion
Rotating field micromotionω
2π (kHz)

450253

E (V/cm)
0.03
0.3
16

Length scale (mm)
2
0.2
0.3

Kinetic energy (K)
30
30
2800

62

4.2

JILA eEDM ion trap version 2

4.2.1

Trap construction

Equipped with the basic knowledge of ion traps and rotating bias fields, we now turn to the
JILA eEDM ion trap. Prior to this thesis work, a first generation ion trap has already been built
and demonstrated to trap HfF+ ions by resolving the mass-to-charge ratios of the ion species[83].
A second generation ion trap needed to be constructed to provide both a uniform rotating fieldand efficient spin readout using laser-induced fluorescence. Given our ability to create HfF+ ionsof a single isotope using photoionization, there was a less pressing need for the second generation
ion trap to exhibit a high mass resolution capability. Instead of isolating different HfF+ isotopes,
all we require is to isolate HfF+ from Hf+ (see Chapter 6).
As demonstrated in Chapter 3, laser-induced fluorescence of ions can serve as a method ofstate-sensitive ion detection. Fig. 4.2a and b show a schematic and photograph of the second
generation ion trap, respectively. Central to the ion trap design are two ellipsoidal mirrors, eachof which focuses light from the trap center to the other mirror’s exit after a single reflection off
the mirror. Light is then directed through light pipes to photomultiplier tubes (PMTs) outside
the vacuum can. The radial extent of each mirror (177.8 mm in diameter) is chosen such that thelargest angle of incidence to the light pipe is 45◦ . The mirrors are held at ground, whereas the lightpipes, being electrically insulated from the mirrors, serve as the end cap electrodes providing axial
confinement in a linear Paul trap. Both the mirrors and light pipes are machined out of aluminum,hand-polished to a mirror finish and coated with gold. The solid angle subtended by the mirrors is
0.6 × 4π steradians and the reflectivity of gold coated on the hand-polished surface is 0.85, making
the combined efficiency of both light pipes capturing light emitted from a 1 cm diameter ion cloudas high as 0.5.
The electrodes responsible for radial confinement of the ions are shaped as fins to minimize
their shadow cast on the mirrors. The shaping of electrodes as narrow fins, however, may compromise the radial field homogeneity [19], thus there are six electrodes instead of four as in a usual

63Paul trap so as to improve the uniformity of the rotating field in the trap center. Nevertheless, thetrapping potential still mimics that of a conventional quadrupole trap, as two pairs of electrodes
are tied to the same RF voltage within the pair (Fig. 4.2c). Each stainless steel, electropolished finelectrode is 8 cm apart from its diagonally opposing fin, and shaped like a parabola to obtain more
uniform fields in the axial direction. The ends of each fin are machined into threaded rods withflat edges to guide the positioning of each fin at a relative angle of 60◦ to its adjacent fins. With
this ion trap design, the rotating field is calculated to have an inhomogeneity of as small as 0.5%
over a 1 cm diameter ion cloud, assuming perfect assembly and trap driver electronics.
The trap confinement coefficients k1 Vec and k2 Vrf can be obtained by simulating the trap
potential in SIMION and calculating the second derivatives of the potential. The center of thequadrupole potential can be approximated as two parabolas of opposite sign, one along x̂ and theother along ŷ. By applying 1 V to fins 2, 3, 5 and 6, and -2 V to fins 1 and 4 while holding the end
cap electrodes at ground (see Fig. 4.2c), the radial trap confinement coefficients along x̂ and ŷ aregiven byk2x Vrf = 595 V/m2 ,(4.24)

k2y Vrf = −603 V/m2 .

(4.25)

Along the axial direction, applying 1 V to the end cap electrodes while holding the radial finelectrodes at ground gives the axial trap confinement coefficients
k1z Vec = 26.1 V/m2 .

4.2.2(4.26)

Trap driver electronics

To drive each ion trap fin electrode, several electronic inputs are used: a quasi-DC voltage thatcan be gated and ramped on and off, a trapping RF voltage at 40–50 kHz, and a rotating voltage at
253 kHz, for which adjacent fins have a 60◦ relative phase shift. The end cap electrodes have the DC
voltage component only. The DC voltages are the buffered output of a 8-channel digital-to-analog

64

(a)

(b)

(c)
Top view of ion trap
Fin 5
Fin 4

Fin 6

Fin 3

Fin 1

Z
5 cm

X

Fin 2

Y

Figure 4.2: (a) Side view schematic of the ion trap. (b) Photograph of the bottom electrodes,
mirror and six fins, taken during a test assembly of the ion trap. In this test assembly, the bottom
end cap electrode had a different cross section profile than the electrode used in the final assembly(see also Fig. 5.1c). (c) Bird’s eye view schematic of the HfF source and ion trap setup.

65
converter (DAC, part number NI6733), which is then passed through a multiplexer comprising aseries of DG409 analog switches actuated by the TTL outputs of a Labview-controlled DIO64. The
multiplexer switch enables the fins to apply either a DC shim voltage for the trap or an electric field
impulse to ‘stop’ or ‘kick’ the ions as necessary. The trapping RF voltage is provided by an Agilent
function generator 33220A, whose output amplitude can be amplified with a voltage-controlled gain
op-amp (AD8336). The voltage-controlled gain op-amp allows the ion trap spring constants to beramped up and down dynamically. Finally, the rotating voltages are applied by six digital delay
synthesizer (DDS) channels (from two synchronized AD8429 chips), with one channel for each finelectrode. Each channel’s amplitude, phase, and frequency are digitally programmed in Labview,
where a ramp of any one of these attributes can be triggered dynamically using TTL. A single DDS
channel output is differentially amplified by an op-amp OP-27, and then amplified with a variable
gain by another OP-27 that uses a multiplying digital-to-analog converter (DAC chip AD5543) as
its feedback resistor. The multiplying DAC and second OP-27 allow for dynamic ramps of therotating voltage amplitude between several different values.
The DC voltage, trap RF voltage and AC-coupled rotating voltages are then sent to the main
ion trap driver to be buffered, summed and then amplified. Fig. 4.3 shows a schematic of the main
trap driver circuit. LM318N op-amps are used for buffering the DC voltages, whereas OPA627
op-amps are used for buffering the trap RF voltages and summing up all the different inputs fora given electrode. The output of each summing OPA627 op-amp is then amplified with a gain of
100 using a PA98 op-amp that is driven by a ±200 V/0.1 A power supply. The PA98 op-amps areattached to a water-cooled aluminum block to manage their heat dissipated. In fact, relay switches(Meder BE05-2A85-P) ensure that the PA98 op-amps can be turned on only if the chilled water isalready flowing. As connected in Fig. 4.3, the PA98 can provide an output voltage of ±200 V andcurrent of 63 mA, and with a gain of 100, its maximal slew rate is at 1000 V/µs.
To drive a large amplitude rotating field at high frequency given the limited output current,
it is important to reduce the capacitive load seen by a PA98. The total capacitance load of a
PA98 is 126 pF, of which 40 pF comes from a radial fin (32 pF) and its two SHV connectors (4 pFInput Rotating Voltage

Ion trap Driver
Buffers

Input DC Voltage
8-channel
DAC

Summing amplifier
Power amplifier

Multiplexer(Presently
unused)Input TrapRF Voltage

Interlocks

Figure 4.3: Schematic of the trap driver inputs and electronics used to generate the voltage applied to a single fin electrode. In the trap
driver, the ‘TRAPX’ and ‘TRAPY’ buffer op-amp outputs are shared amongst 4 and 2 fin electrodes, whereas the ‘SEC’ and ‘DC’ buffer
op-amps, summing amplifier and power amplifier are repeated 7 more times for all 6 fin electrodes and the 2 end cap electrodes.
6667each), whereas the remaining capacitance comes from using a 183 cm RG-62 cable to connect the
PA98 output to a fin electrode. To monitor an electrode’s voltage while minimizing the oscilloscopeprobe’s capacitance seen by the PA98, 1% of each PA98 output is tapped off using a voltage divider
and sent through a buffer (not shown in Fig. 4.3). With these capacitive loads, the PA98s canprovide a rotating field of up to ±24 V/cm (from ±150 V applied, so that 50 V is reserved for Vrf )at 300 kHz without significant distortion.

4.2.3

Experiment sequence for ion trapping

Putting the trap electrodes and driver electronics altogether, the ion trap as used in theeEDM experiment is typically driven as described in the following sequence (see also Fig. 4.4a) anddiscussed in more detail in Section 4.3.
(1) Neutral HfF molecules are created in the source chamber, as already described in detail in
Chapter 2. The neutral molecules undergo supersonic cooling to a rotational temperatureof ∼10 K as they traverse a differentially pumped chamber into the ion trap chamber. The
ion trap chamber does not have any vacuum pumps directly attached to it, although it is
attached (with a conductance of 420 l/s) to a nearly empty adjacent six-way cross with a
Varian TV551 turbo pump mounted on top.
(2) The cooled cloud of neutral HfF molecules, entrained in the argon buffer gas, are excited
via optical-optical double resonance to a Rydberg state and autoionized in-trap. The ionsinherit the 600 m/s center-of-mass velocity of the neutral beam.
(3) The trap electrodes apply an electric field along -x̂′ to stop the HfF+ ion beam in the centerof the trap.
(4) The trap RF voltages (along with any DC shims for the radial fins) and end cap voltages
are immediately turned on to start confining the ions.
(5) (Optional) The amplitude of the rotating field is ramped on, held fixed for a given duration,

68
and then ramped back down to zero.
(6) (Optional) The trap RF voltages and end cap voltages may also be ramped up over timeto provide a more or less tightly confining trap as necessary.
(7) When the trap confining voltages are turned off after a given trap duration, a uniform
electric field is applied along x̂, x̂′ or −x̂ to ‘kick’ the ions onto one of the two ‘fast’
microchannel plate assemblies (MCPs) or onto an ‘imaging’ MCP, which is a phosphor
screen located behind two stacked microchannel plates. These MCPs allow us to diagnose
the ions’ in-trap motion in the x̂, ŷ and ẑ directions.
Fig. 4.4b shows the sequence of voltages applied to one of the fin electrodes (fin 3) for the last four
steps. The following section details our efforts to optimize the trap loading and characterize theion trap.

4.3

Trap loading and characterization

4.3.1

Basic assumptions and terminology

Before launching into a presentation of our trap optimization and characterization techniques,
we first lay out the assumptions we often make when considering the ions’ motion in the trap. For
an individual ion, its simple harmonic motion in the trap is independent of other ions. This meansthat an ensemble of trapped ions behave roughly like an ideal gas, where the mean field energy andcollisions are both small. The mean free path of an ion between collisions is very long comparedto the size of the ion cloud, such that in a 3-dimensional harmonic trap with incommensurate trap
frequencies ωx 6= ωy 6= ωz , the motion along each direction is separate.
Formally, the secular motion of the ith ion in the j th direction can be expressed asrji = Aij cos(ωj t + φi ) ,(4.27)

where ωj is the trap frequency along the j th direction. We assume the following distributions for

69

(a)

Differential
Source pumping
chamber chamber

Ion trap chamberabcd abcd abcd abcd abcd abcd abcd abcd abcd abcd
abcd abcd abcd abcd abcd abcd abcd abcd abcd
bacd abcd abcd abcd abcd abcd abcd abcd abcd abcd
Fin 5abcdabcdabcdabcdabcdabcdabcdabcdabcdabcdabcdabcdabcdabcdabcdabcdabcdabcdabcd
abcd abcd abcd abcd abcd abcd abcd abcd abcd
abcd abcd abcd abcd abcd abcd abcd abcd abcd abcd
abcd abcd abcd abcd abcd abcd abcd abcd abcd
abcd abcd abcd abcdFin
abcd abcd abcd abcd abcdImaging
abcd
abcd abcd abcd abcd abcd6 abcd abcd abcd MCP
abcd

Ionization
lasersAblation
laser

Skimmers

Fin 4

Ar (99%) +SF6 (1%)

Hf

Hf
Pulsedvalve-Vrf cos (wrft)

F
Fin 1

bacd abcd abcd abcd abcd abcd abcd abcd abcd abcd
2Vrf cos (wrft)
abcd abcd abcd Fin
abcd abcd3abcd abcd abcd abcd
abcd abcd abcd abcd abcd abcd abcd abcd abcd abcd
abcd abcd abcd abcd abcd abcd abcd abcd abcd
abcd abcd abcd abcd abcd abcd abcd abcd abcd abcd
abcd abcd abcd abcd abcd abcd abcd abcd abcd Fin 2
abcd abcd abcd abcd abcd abcd abcd abcd abcd abcd
“Fast”
abcd abcd abcd abcd abcd abcd abcd abcd abcd
MCP
abcd abcd abcd abcd abcd abcd abcd abcd abcd abcd
abcd abcd abcd abcd abcd abcd abcd abcd abcd

(ms)

‘Stop’ pulse
Fin 3
output (V)

(b)

Hf+

F

Rotating field

Trap

Y’
Z
X

dcab cdab cdab cdab cdab cdab
cdab cdab cdab cadb cdab
cadb cdab cdab cadb cdab cdab
cdab cdab cdab cdab cdab
cdab cdab cdab cdab cdab cdab
cdab cdab cadb cdab cdab
X’cdab cdab cadb cdab cdab cdab
cdab cdab cdab cdab cdab
cdab cdab cdab cdab cdab cadb
cdab cdab cdab
Y cdabcdabcadbcadb“Fast”
cdab cdab cdab cadb
cdab cadbMCP
cdab cdab 2cadb

Final pumping
chamber‘Kick’ pulse

0
-200
0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0.2

Figure 4.4: (a) Bird’s eye view schematic of the HfF source and ion trap setup. In the ion trap
chamber, HfF+ are formed in-situ by autoionization, trapped, and then ejected onto one of thethree diagnostic MCPs, which allows us to detect both the ion number and motion in-trap. The
top and bottom end cap electrodes are not shown. (b) Voltage output on one of the radial finelectrodes (fin 3).

70
the phase φ and amplitude A for a cloud of ions:(a) f (φ) is uniform,
2

2

A
− mω
k T

(b) f (A) ∝ Ae

B,

(4.28)

where mω 2 A2 is the total (kinetic and potential) energy of the ions and T is the temperature of
the cloud. A note of caution is that these assumptions are not necessarily valid, but we make themfor their simplicity.
The overall motion of the ion cloud can be described in terms of a ‘slosh’ and ‘breathe’ if thefollowing occurs:
f (φ) 6= f (φ + π) (sloshing) ,f (φ) + f (φ + π) 6= f (φ +π
3π
) + f (φ +) (breathing) .
2
2

So far, we have also assumed that the trap is perfectly harmonic. In the presence of trap anharmonicities or ion-ion collisions, φj randomizes and the cloud can spread out as the sloshing andbreathing can transform into a hotter cloud.
Experimentally, the slosh and breathe are characterized by motion in the center-of-mass of
˙ and a change in the cloud radius (σ r , σ ṙ ), respectively. In the absence of breathe,the cloud (r̄, r̄)σṙ = ωσr . The ion cloud temperature TJ along the j th trap direction can also be inferred from thecloud width σj :
Tj =

m 2
m
vj =
(ωj σj )2 .
kB
kB

(4.29)The slosh and breathe can in turn be combined with the cloud width into an effective width σeff,j :σeff,j =q22 ,σj2 + σCM,j+ σb,j(4.30)

where σj is the spread of individual ions’ secular motion averaged over the cloud with the distribution given by Eq. (4.28), σCM,j is the root-mean-squared slosh amplitude, and σb,j is the
root-mean-squared breathe amplitude.

71
4.3.2

Trap loading

In many ion-trap experiments [29, 49], the ions are created using electron-gun ionization or
photoionization, and then cooled via laser cooling or sympathetic cooling to 10–100 of µK upon
being trapped. The eEDM measurement, however, can be performed with the HfF+ ions being as
hot as 10–30 K [45]. When the HfF+ ions are initially created via autoionization, their translationaltemperature (in the moving frame) is the same as that of the supersonically cooled molecular beam,i.e. 10 K. No further cooling of the ions is then required during the trap duration as long as the ionscan be brought to a stop from 600 m/s without additional heating, and the RF heating within theion trap occurs on a time scale long compared to the eEDM measurement. After stopping the ions,the loading of the ion trap is considered optimal if the effective spatial width σeff,j as described by
Eq. (4.30) is dominated by σj . Since each contribution to the width is added in quadrature, as longas σCM,j and σb,j are less than a third of σj , their contribution to the effective width is about anorder of magnitude smaller than σj .
All three contributions can be measured simultaneously by looking at the ions’ arrival on the‘imaging’ MCP (for motion along the trap axes ŷ, ẑ) or the ‘fast’ MCP housed in the same trap
chamber (for motion along the trap axis x̂) as a function of the trap duration. Measurements ofthe slosh and breathe tend to be made at short trap times (i.e. after only a few trap cycles), where
the slosh and breathe, if their amplitudes are discernible, are expected to take place at the trap
frequency and twice the trap frequency, respectively. At longer trap times, the slosh and breathe
amplitudes may be diminished if the ions interact with each other or with trap anharmonicities andcause dephasing. Fig. 4.5a shows a typical set of slosh, spatial width and breathe data measured
along the x̂ axis on the ‘fast’ MCP over a few trap cycles, where each data point is obtained byfitting the time-of-arrival distribution of the ions on the ‘fast’ MCP to a Gaussian distribution andrecording its center and standard deviation. In the plotted example, the trap loading is sub-optimal
since the slosh amplitude is three time that of the spatial width.
To achieve optimal loading with minimal slosh, two conditions need to be met: firstly, the72
ion cloud’s center-of-mass velocity needs to be removed, and secondly, the position at which theions come to a stop (from 600 m/s) needs to be the same as that when the ions are close to thetrap center. More precisely, the distance between the position at which the ions come to a stopand the trap center determines the slosh amplitude. To meet the first condition, the ‘stop’ electricfield pulse applied opposite to the center-of-mass velocity needs to give the correct impulse to theion cloud, and can be varied by changing the amplitude-duration product of the pulse. To meetthe second condition, the DC shim voltages of the ion trap center need to be adjusted. Since theprincipal trap axes are a linear combination of the direction of center-of-mass velocity x̂′ , the above
two conditions must be fulfilled in both the x̂ and ŷ directions (see Fig. 4.4a). To optimize this twodimensional walk of parameters for a given trap axis (say, x̂), we can plot the real and imaginaryparts of the ions’ slosh as obtained from Fig. 4.5a as a point on a complex plane (Fig. 4.5b), wherex = Ax cos(2πφx ), y = Ax sin(2πφx ). Varying the ‘stop’ pulse walks the points on the complex
plane along the direction û, whereas adjusting the DC shims walks the points along v̂. Using thisinformation, once we figure out where a point describing a given slosh behavior lies on the complex→
plane −
w = |u|û + |v|v̂, we can easily minimize the slosh by jumping it towards the origin of thecomplex plane.
The breathe of the ion cloud can be minimized by matching the in-trap temperature to theinitial temperature of the moving cloud, i.e. the trapping potential energy and initial kinetic energy
are close to the equal partition point. If the trap is too tightly confining for the initial temperature,
the ion cloud will breathe inwards at the start of the trap. Conversely, if the trap is too weakly
confining for the initial temperature, the ion cloud will initially breathe outwards. The typical trap
frequencies are about ω = (2π)3–6 kHz.
All of the above slosh and breathe measurements of the ion cloud have been taken with the RFcomponent of the trap voltages set to a particular initial phase φrf , e.g. VF inX = −Vrf cos(ωrf t+φrf ).
At different times within a RF cycle, the speed of the micromotion can vary between zero andeE(x0 )/(mωrf ), where x0 is the position of maximum displacement from the trap center. (Thedisplacement of micromotion may be ignored because it is typically about a tenth of the secular

73
displacement, as shown in Table 4.1.) The RF initial phase φrf is then chosen such that at the startof the trap, the least amount of micromotion velocity is excited. Similarly, when the ion cloud is‘kicked’ out of the trap towards one of the diagnostic MCPs, the RF end phase is chosen so thatthe micromotion velocity does not add to the overall velocity, and the spread of ions on the MCP
is solely due to the ions’ secular motion. In other words, where φrf is set to minimize the excitationof initial micromotion velocity, the trap duration Ttrap is chosen such that ωrf Ttrap = 2πn, where
n is a positive integer.

4.3.3

Microchannel plate transfer matrices

In the previous section, we have only tried to minimize the slosh and breathe relative tothe width of the ion cloud as detected on the MCP. Ultimately, however, we are interested in thewidth of the ions in-trap σtrap,j . The width of ions on the detector may be scaled down or up fromthe in-trap width, depending on whether the ions get focused or de-focused on their way to thedetector. Further, the distribution of ions on the MCP may reflect either the position or velocity
distribution of ions in-trap, or some linear combination of the two, depending on how long theions take to travel towards the detector compared to a trap oscillation. For many atomic physics
experiments using time-of-flight expansion to probe the atomic cloud width, the atoms take a longtime to fall to the detector, so the cloud width as seen on the detector is mainly due to the in-trap
velocity distribution . Conversely, one can imagine applying a very high electric field pulse topush ions towards a nearby MCP such that the flight time Tdet is much shorter than a trap cycle(ωj Tdet ≪ 1), in which case the in-trap position distribution gets ‘frozen’ out and is projected (upto some scale factor) directly onto the MCP.
To figure out how the width as seen on the detector maps onto the in-trap width, we assume
that the trapped ions undergo small displacements about the trap center, so that any change inthe position or velocity remains linear. We can then use the following transfer matrix formulation:




 

 ztrap   m11,z m12,z Tdet,z   ztrap  zdet (4.31)
 = Mz 


=
.
żtrapωz ztrapżdet
m21,z m22,z Tdet,z74

x = x0 + Ax sin (ωx t + φx)
C.M. arrival
time (µs)

37x = 34.5 µs, A =0.638 µs,
0xω =(2π)6.4 kHz, φ =(2π)0.861

36

x

x

35
34

0.24

σions (µs)(b) 0.2

0.22
0.2
0.18

5

0.1

Im[x−slosh] ( µs)

(a)

0
−0.1
−0.2

6

v̂

−0.3
−0.4

4

û

−0.5

0.16
1

1.1

1.2

1.3

Trap Time (ms)

1.4

1.5

−0.6
−0.2

3
0

1

2
0.2

0.4

0.6

Re[x−slosh] (µs)

Figure 4.5: Motion of trapped HfF+ ions along x̂, where the position and width of the ions are
mapped onto arrival time on the ‘fast’ MCP in microseconds. (a) (Top) The center-of-mass slosh of
the ion cloud versus trap duration is fit to a sine wave, from which the trap frequency is extracted tobe (2π)6.4 kHz; (bottom) standard radius of the ion cloud as a function of trap duration. While thebreathe of the ion cloud is negligible in this case, the center-of-mass slosh is significant comparedto the standard cloud width, indicating sub-optimal loading conditions. In fact, its slosh amplitude
and phase can be summarized as a single point on a complex plane (point ‘1’) in (b). (b) A summaryof different slosh behaviors for different trap loading parameters. Varying the voltage pulse usedto ‘stop’ the 600 m/s HfF+ ions walked the slosh summary points along û, whereas changing theposition of the DC trap center moved the slosh summary points along v̂.

75
By denoting żtrap = ωz ztrap in Eq. (4.31), we also assume that there is no breathe. The goal is toexperimentally determine the matrix elements m11,j and m12,j of the transfer matrix Mj . m21,jand m22,j are not evaluated because the MCPs do not give the velocity distribution of ions uponhitting the detector. Using Eq. (4.31), the width of the ions as seen on the detector σdet is thenrelated to the in-trap width σtrap via a factor mσ,j :σdet,j = mσ,j σtrap,j =q(m11,j )2 + (m12,j Tdet,j ωj )2 σtrap,j(4.32)

To figure out m11,z and m12,z , we applied a ‘kick’ of known impulse to the ions along theẑ direction and measured the slosh response of the ions as seen on the ‘imaging’ MCP (Fig. 4.6).
Any immediate displacement of the ions came from the change in velocity due to the impulse, as
indicated by the blue dashed line ending with a blue cross in Fig. 4.6. On the other hand, the ions’displacement after a quarter of a trap cycle reflects the change in position effected by the impulse
kick, as indicated by the blue dotted line ending with a blue triangle. In the depicted case, after
an applied voltage kick of 120 Vµs between the top and bottom electrodes, we expected the ions toslosh with an amplitude of 1.76 mm based on SIMION calculations. Since the changes in positionand velocity showed up as a displacement of 1.45 mm and 2.28 mm on the MCP respectively, thetransfer matrix elements m11,z and m12,z are 0.824 and 1.30 for a flight time of Tdet = 0.045 ms tothe ‘imaging’ MCP. The above procedure of measuring the ions’ response to a voltage ‘kick’ can also
be applied to the x̂ and ŷ directions. Table 4.2 summarizes the transfer matrix elements and mσvalues for typical trap frequencies and detector flight times in all three directions. Equipped withthe transfer matrix elements, we can then characterize the ion trap in terms of its patch charges
and anharmonicities by determining how the ions respond in-trap to various voltage settings.

4.3.4

Trap characterization I: patch charges

Patch charges can be easily introduced if there was any grease left on the trap electrodes when
the trap was assembled, or can develop over time if hafnium or other additional material was slowly
deposited on the electrodes. Of the effects that patch charges can have on the ions, the two that we

76

Z C.M. position(mm)Kick4

Post kick: z = z0 + Az sin(ω (t−tkick) + φz)

Az = 2.7(1), z0 = −1.03(7), ωz = (2π) 2.614(1) kHz, φz = (2π) 0.659(9)

2
0
−2
−4
1

2

3

4
5
Trap time (ms)67

Figure 4.6: To extract the ions’ motion in-trap from that on the MCP, a deliberate kick is applied
to the ions (shown here in the ẑ direction) and the resultant slosh response is fit to a sine wave.
The displacement at tkick and at a quarter trap cycle after tkick , given by the dashed line down tothe cross and the triangle, respectively) then maps onto a change in velocity and position due tothe applied impulse. By comparing the expected and measured slosh response, we can deduce the
MCP transfer matrix elements.

77
Table 4.2: Summary of MCP transfer matrix elements and mσ values for typical trap frequencies
and detector flight times in all three directions. m11 , m12 and mσ are dimensionless for the directionsŷ and ẑ, and have units [µs/mm] for x̂.

xyz

Detector‘Fast’ MCP‘Imaging’ MCP‘Imaging’ MCP

m11
0.129
0.412
0.824

m12
0.093
1.60
1.30

Tdet (ms)
0.021
0.045
0.045

ω
2π (kHz)

5.9
4.2
3.7

mσ
0.148
1.94
1.59

care most about are dipolar and quadrupolar effects. Dipolar patch charges (simulated as +Vpatch
and −Vpatch on two opposing electrodes) can displace ions away from the ion trap center, while
quadrupolar patch charges (simulated as +Vpatch on each of the two opposing electrodes) can modify
the trap frequencies relative to that expected from SIMION calculations. By characterizing patch
charges, we can understand how closely the resultant ion trap potential resembles that calculated
from SIMION when the effects of patch charges are accounted for, which may (or not!) indicate
whether the ion trap assembly is built as a faithful realization of its design. Further, it is importantto null out dipolar effects so that the ions do not shift in position over time.
Along the ẑ direction, both dipolar and quadrupolar patch charges can be simultaneously
quantified by first trapping the ions, and then adiabatically ramping up or down the axial confinement to avoid exciting a large slosh. The ions’ center-of-mass motion along ẑ is measured on the‘imaging’ MCP for a few oscillation cycles and both the post-ramp offset and axial frequency arerecorded. In the presence of a dipolar patch electric field Ez,patch , the ions shift to a new position
z0 :
Uz =
=
⇒ z0 =

1mωz2 z 2 − qEz,patch z
2




qEz,patch 2
qEz,patch 2 1
12+ mmωz z −
2mωz2
2
ωzqEz,patch.
mωz2(4.33)

Fig. 4.7a shows how the post-ramp offset varies with axial frequency. The dipolar patch field canbe extracted from the slope of the fit in Fig. 4.7a, which in this case turns out to be -0.21(3) V/m.

78
To elucidate the quadrupolar patch field ∂Ez,patch /∂z, we can examine the trap axial frequency
instead. Fig. 4.7b shows how the square of the axial trap frequency, rescaled by ωrf , varies against
the trap parameter a, where a can be calculated given the specified DC voltages applied to the end
cap and fin electrodes. Using Eq. 4.18b, we expect the data points to fall on a line of slope -2, andany offset is attributed to a quadrupolar patch field:
ωrf p
ωz =
−2a + apatch
2

2
2ωz
⇒
= −2a + apatch ,ωrf
2e ∂Ez,patch
where apatch =
.
2
∂z
mωrf

(4.35)(b) 0.025−0.8Ez,patch = -0.21(3) V/m∂Ez,patch= 90(20) V/m2
∂z

0.02
2

−1
rf

(2ω / ω )

−1.2

0.015

z

Displacement in trap (mm)(a)(4.34)

−1.4

0.01

−1.6
0.005

−1.8
−2

0.2

0.4
2
−2
1/f (kHz )
z

0.6

0

−0.01

−0.005a0zFigure 4.7: (a) The ions’ in-trap displacement is measured as a function of the inverse trap frequency
squared, from which the slope yields the axial dipolar patch field Ez,patch . (b) The ratio of trap
secular frequency to the RF frequency, squared, is plotted against the applied end cap electrodevoltage (proportional to az ). The slope is fixed to be -2, in accordance with Eq. (4.34), and theoffset indicates the quadrupolar patch field ∂Ez,patch /∂z.
For the radial directions, a dipolar patch electric field would not only displace the ions (thedisplacement is more apparent if the DC potential is weak compared to the pseudopotential), butalso induce excess micromotion arising from the non-zero RF voltages at the center of the DC

79potential [8]:qx
x = (x0 + Ax sin(ωx t + φx )) 1 +cos(ωrf t) ,2

(4.36)

where x0 is the displacement described by Eq. 4.33 for the patch field Ex,patch . The micromotion
qx x0 /2 is considered to be in “excess” of the regular micromotion that has zero amplitude when theions are at the trap center but whose amplitude increases when the ions move away from the trap
center. To determine the radial dipolar patch field, we can probe the micromotion amplitude when
the ions are displaced by an equal amount from the trap center. How these ion in-trap positions
map onto the detector positions have already been determined from the MCP transfer functions
as outlined in Sec. 4.3.3: in Fig. 4.8, for instance, ions at positions ‘1’ and ‘2’ correspond to ionsthat are displaced farthest from and nearest towards the ‘fast’ MCP, respectively. Where there isa dipolar patch field Ex,patch displacing the ions away from the detector, the micromotion of ionsat position ‘1’ is larger than those at position ‘2’, as shown in Fig. 4.8a. In Fig. 4.8b, the patch
field has been compensated for by applying DC shim voltages to the fin electrodes, such that the
micromotion measured at the two equal displacements display the same amplitudes.

4.3.5

Trap characterization II: anharmonicities

To lowest order, the confinement of ions in an ion trap is harmonic with a trap frequencyof ω0 . However, once the ions access larger displacements from the trap center, anharmonic terms(e.g. bz 4 ) in the trapping potential Φ start to matter. Anharmonic terms can modify the observed
trap frequency ω, depending on the ions’ oscillation amplitude z:


1
2bz 2
1
2 2
4
2 2
mω0 z + bz = mω0 z 1 +
U =
2
2
mω02
1
≡
mω 2 z 2
2 s


2bz 2
bz 2
⇒ ω = ω0 1 +≈ ω0 1 +mω02
mω02(4.37)The JILA eEDM ion trap was designed to have the anharmonic contribution be as small as
1.2% over a trap radius of 1 cm to minimize systematic effects in measuring the eEDM signal. An

80

60

60

Arrival time ( µs)

(a)

(b)

1

55

1

55
2

2

50

50

45

45
1

1.2
Trap time (ms)1.4

Position of 0
micromotion‘Fast’MCP

1
DC trap2

1

1.2
Trap time (ms)‘Fast’MCP

1
AC trap

1.4

2

DC trap
AC trap

Figure 4.8: Plots of micromotion (red data points, 1 period = 25 µs) at different trap positions(secular motion shown in blue): at position ‘1’ (‘2’), the ions are displaced farther from (nearest
towards) the ‘fast’ MCP detector. (a) A dipolar patch field has displaced the ions away from thecenter of the harmonic pseudopotential formed by the RF voltages (denoted as ‘AC trap’), so themicromotion tends to be larger at position ‘1’ than at ‘2’. (b) When the dipolar patch field is nulled
out, the micromotion is equal at both positions ‘1’ and ‘2’.

81
experimental determination of the trap anharmonicities would not only check the trap assembly
configuration against its design parameters but also help us (together with other measured quantities) estimate systematic effects for the eEDM measurement. To measure the trap anharmonicity,
we kicked the ions along the axial direction and measured its resultant slosh amplitude and frequency. Fig. 4.9 shows a summary of the trap frequency dependence on the slosh root-mean-squareamplitude, from which the anharmonic contribution to the frequency is determined to be 1.7% overz

Slosh z frequency f (kHz)a trap radius of 1 cm.

2.64

f = 2.6 kHz
02−2b/(mω ) = 0.0173 cm

2.63

0

2.62
2.61
2.6
2.59

0

0.2

0.4

0.6

0.8

Slosh zRMS amplitude (cm)Figure 4.9: Plot of slosh frequency versus root-mean-square amplitude, where the different slosh
amplitudes have been excited by kicking the ions. The blue data points are fit to a curve given by
Eq. (4.37).

4.4

Rotating field characterization
Many of the tools already developed in Section 4.3 are directly applicable to the character-ization of the rotating bias electric field. A characterization of the rotating field inhomogeneity is
not purely an academic exercise, but has profound implications on potential systematic effects forthe eEDM experiment. Briefly (see [45, 83] for details), if Erot was always larger in the region z > 0than that in z < 0 by 0.03%, a frequency shift of ωmax = 0.0003 δmF ωrotEz,maxErot≈ (2π)0.23 Hz

would be added to the energy difference between the two Zeeman sublevels |ai and |bi in a single
3∆

1 Stark manifold (see Fig. 1.5). The net systematic effect after performing the four-way eEDM

chop described by Eq. (1.7) is then a frequency shift of (δgF /gF )ωmax = (2π)0.45 mHz, which

82
translates to a systematic error of δde = 9 × 10−30 e cm. These values assume ωrot = (2π)250 kHz,Ez,max = 1 V/cm, Erot = 10 V/cm and δgF /gF = 0.002.
Although the rotating field is applied in the (x̂, ŷ) plane, inhomogeneities in Erot along x̂ andŷ transform into an inhomogeneity along ẑ by Laplace’s equation:~ · E~rot = 0∇⇒∂Erot ∂Erot
∂Erot
=−
−
.
∂z
∂x
∂y

(4.38)

Further, if the axial direction is not orthogonal to the plane of rotation, one can obtain highern

order spatial dependencies of Erot in the axial direction, i.e. ∂∂EEnrot 6= 0. Expressing the rotatingrotfield inhomogeneity as a Taylor expansion in z, we get
1 ∂ErotErot
1 1 ∂ 2 Erot 2
=
1
+
z
+
z + ... ,000∂z
2 Erot
∂z 2
Erot
Erot

(4.39)

0 is the nominal value of the bias field.
where Erot

In the presence of an inhomogeneous rotating field, the ions experience a ponderomotive force
that causes the ions to undergo secular motion in addition to its circular micromotion, like that
described in Section 4.1.2. Analogous to Eq. (4.8), the ponderomotive potential energy eD̄rot (X̄)
is the same as the kinetic energy Urot given by Eq. (4.23). The total potential energy experienced
by the trapped ions in an inhomogeneous rotating field is then

e2
1
1
2
2
2
m
ω
+
(∆ω)
(z − z0 )2 .
E=
U = mω02 z 2 +
0
rot
2
2
2
2mωrot(4.40)The effect of Urot on the ions’ secular motion is described by a mean displacement z0 and aquadrature difference in secular frequency with and without a rotating field (∆ω)2 . The first order
gradient in Erot can be extracted from z0 :∂U
∂z⇒1 ∂Erot
0
∂z
Erot


∂Erot
e2
Erot
= m ω02 + (∆ω)2 (z − z0 )
2
∂z
mωrot

2
mωrot ω0
≃
z0
0
eErot

2 
2 

ω0
1 V/cm 2  z0 
ωrot
= 4.3
(2π)253 kHz(2π)1 kHzErot
1 cm
= mω02 z +cm−1 ,(4.41)

83
where the (∆ω)2 term can be neglected. A further round of differentiation yields the expression
for the second order gradient:∂ 2 Erot∂z 2
1 ∂ 2 Erot
0
∂z 2
Erot

"
2 #
2
 2
2

e
∂E
∂
E
rot
rot
2
2
0
=
m
ω
+
(∆ω)
= mω02 +
+
E
0
rot
2
∂z
∂z 2
mωrot


mωrot 2
≃
(∆ω)2
0
eErot

2 


1 V/cm(∆ω)2ωrot
cm−2 .
= 4.3
0(2π)253 kHz((2π)1 kHz)2
Erot(4.42)To experimentally characterize the rotating field inhomogeneity, the ions’ secular motion ismonitored with and without a rotating field. For the case with the rotating field present, Erot needs
to be ramped on quickly compared to a cycle of secular motion but slowly compared to the rotation
frequency ωrot to avoid kicking the ions. Erot is ramped off at the same speed as its turn-on ramp,
at a short but fixed time interval before the end of the trap duration. Fig. 4.10 shows the ions’mean displacement and secular frequency, as detected on the ‘imaging’ MCP, plotted as a functionof Erot . The plotted mean displacement has already been converted into the in-trap displacement
using the MCP transfer matrix. Using Eq. (4.41), the first order inhomogeneity E 01

rot

∂Erot
∂z z over a

typical cloud 2σ-radius of z = 3 mm is 6(1) × 10−5 . Similarly, from Eq. (4.42), the second orderinhomogeneity in Eq. (4.39) over z = 3 mm is measured to be 1.0(1) × 10−4 .

4.5

Fluorescence
So far, the trap and rotating field characterization results have implied that the JILA eEDM

ion trap is fairly well-matched in its assembly compared to its design. How well the ion trap performs
in terms of ion fluorescence collection, which is one of the trap’s major design considerations, has
yet to be seen and will be presented in the following chapter.

84

−3

(a)

x 10
3
2.5

z0
(V/cm )2
= 3.6(8) × 10−6
2
Ero
cm
t

0

z (cm)

2
1.5
1
0.5
0
−0.5

(b)

q
2 + (3.59kHz)2
βEro
t
2π
¶2
µ
kHz
β = 5.4(5) × 10−4
V/cm
³ ω ´2
z

3.64

=

3.62

z

ω /(2π) (kHz)

3.66

3.6
3.58

0

5

10

15

20

25

Erot (V/cm)

Figure 4.10: (a) Plot of mean displacement versus Erot , from which the quadratic term can be used
to determine the first order gradient in Erot . (b) Plot of secular frequency versus Erot , from which
the second order gradient in Erot can be extracted.

Chapter 5
Spin readout techniques (I): fluorescence

The ability to detect HfF+ in a state-sensitive manner is an integral part of the eEDM
measurement: in the Ramsey spectroscopy of an eEDM-sensitive transition, the transition frequency
is measured by counting the relative HfF+ left in one of the two spin states as a function of the freeevolution time between two π/2 pulses. In the context of Ramsey spectroscopy, the state detection
process is also known as the spin readout process.
Before beginning the Ramsey pulse sequence, state-sensitive detection of HfF+ is also used todetermine the number of ions prepared in the desired state. As shown in Chapter 3, we have alreadydemonstrated the ability to detect the rotational states of HfF+ using laser-induced fluorescence(LIF), so it is tempting to extend that to LIF in-trap, as discussed in this chapter. It is important
to bear in mind that LIF is not used as the final means of state detection for the eEDM experiment,
especially with the development of resonance-enhanced multi-photon dissociation (REMPD) as astate detection method that is two orders of magnitude more efficient than LIF (see Chapter 6).
Nevertheless, this chapter discusses the design considerations behind the incorporation of LIF with
an ion trap, with the aim of maximizing fluorescence photon collection while minimizing scattered
light. At the end of this chapter, we also present estimates for cavity-enhanced absorption as aplausible state detection technique.

86

5.1

Experiment setup

5.1.1

Fluorescence collection

The LIF that is performed on the trapped ions makes use of the same transitions as that on
the molecular beam in Chapter 3: a 1 µJ/pulse laser at 769 nm (output by a dye cell amplifier seededby a diode laser) drives a rotational transition in the 1 Π1 ←1 Σ+ (ν ′ = 0, ν ′′ = 0) band [16, 81], andfluorescence photons emitted on the 1 Π1 →1 Σ+ (0, 1) band are detected by a photomultiplier tube
(PMT). As with almost all molecular transitions, this one is non-cycling, which means that once amolecular ion gets excited by a 769 nm photon and fluoresces, it lands in a dark state and cannot
be re-excited by the same laser on the LIF experiment time scale. Hence, the in-trap fluorescencecollection setup, comprising two large gold mirrors as detailed in Chapter 4, was built to capture
photons with as high an efficiency as possible.
By design, most of the photons exit the light pipe onto a PMT with an angle of 45◦ , favoring a
PMT with the photosensitive material close to its flat entrance surface (e.g. Hamamatsu R7600U20-M4) as opposed to one with a curved glass surface, from which the photosensitive material
is farther recessed (e.g. Hamamatsu R3896). Since the preferred PMT (R7600U-20-M4) has asquare-shaped active area (18 mm × 18 mm), the light pipe also has a matching square profile(11 mm × 11 mm) (see Fig. 5.1). The use of R7600U-20-M4 over R3896, however, comes at a
price: the quantum efficiency of the photosensitive material is 5% and 15% at 818 nm for theformer and latter PMT, respectively. In fact, both PMTs are specified to have the same quantum
efficiency curves, but the R3896 has been measured to have an uncharacteristically high quantum
efficiency. Nevertheless, the overall efficiency of fluorescence photon collection with the ion trap
setup described so far in combination with two R7600U-20-M4 PMTs is still higher (2.6%) thanthat for the ion beam (1.2%).

87

(a)

(b)

(c)

Photosensitive
material

Figure 5.1: Schematic of a light pipe used in combination with (a) a PMT of curved entrance glass
surface, where the photosensitive material is farther recessed, and (b) a PMT of a flat entrance
surface, where the photosensitive material is nearer to the light pipe. (c) Photograph of the exit ofa light pipe whose square profile matches that of the R7600U-20-M4 PMT.

88
5.1.2

Scattered light, the nemesis

Despite the fact that LIF had already worked for us in a molecular beam, in-trap LIF is notwithout its challenges. Performing LIF in the presence of a ‘shiny’ environment — where the trap
electrodes and large gold mirrors have been polished to a highly reflective finish — means that it
is also easy for scattered light to make its way to the PMT! To optimize the LIF signal-to-noise
ratio, one must try to suppress the the background noise coming from scattered photons.
Scattered light is typically suppressed using three approaches: time gating, wavelength filtering, and spatial filtering. Time gating in the LIF context means that the chain of high voltages
within the PMT circuit is only turned on after the 769 nm laser fires, so that the avalanche process
converting prompt scattered light into voltage pulses is suppressed when the excitation laser fires(Fig. 5.2a). Even if HfF+ had a cycling transition, the need for time gating also eliminates thepossibility of collecting multiple photons from any single trapped ion by shining on the LIF laser
continuously.
Wavelength filtering is carried out by detecting the fluorescence photons at a different wavelength (818 nm) from the excitation wavelength (769 nm). When performing LIF on a molecular ion
beam, we were able to efficiently filter out 769 nm light by placing a narrowband (10 nm FWHM,
820 nm center wavelength) dichroic filter in a region where the light rays were perpendicular to thefilter. With the ion trap setup, however, photons exit the light pipe at a range of angles from 0◦
to 45◦ . Since the transmission of a dichroic bandpass filter tends to be blue-shifted as the angle ofincidence increases (Fig. 5.2b), the 820 nm bandpass filter would both step on the transmission of
818 nm light and ineffectively filter out 769 nm light. Unlike dichroic filters, colored glass filters do
not suffer from any sensitivity to the angle of incidence and are also highly transmissive in their
passband (>90%). However, they tend to refluoresce after absorbing photons in the filter stopband,and the band edge separating the stopband and passband regions is typically as broad as ≈100 nm.
A hybrid of the above two types of filters is the “colored glass alternative” dichroic long-pass filter,
which offers a high transmission in the passband and a relative sharp (10 nm width) band edge,

89
although the band edge width and position can also be tuned by the angle of incidence (Fig. 5.2c).
Such a filter (Newport CGA830) with a nominal band edge at 830 nm is placed between the lightpipe and the PMT to allow for high transmission (>90%) at 818 nm while stepping on scattered
light at 769 nm after accounting for the distribution of angles of incidence.
Besides the 769 nm laser, the much stronger UV pulsed laser (∼1 mJ/pulse, 368 nm) used
to ionize neutral HfF can also give rise to scattered light. (The other ionization laser at 309 nm
has < 10 µJ/pulse.) The UV scattered light could in principle be suppressed by time gating if theionization lasers were to fire a long time before the LIF pulse was applied. However, experiments
probing the rotational lifetime of the molecules need to perform LIF starting from very short times
after ionization, i.e. where time gating alone is insufficient to deal with scattered photons fromthe intense ionization laser pulse. Further, the stray UV photons hitting metal surfaces off thevacuum chamber or ion trap tend to be absorbed and reemitted as red-detuned photons over alarge wavelength range. In this respect, the aforementioned CGA830 long-pass filter helps to filterout scatter from the UV laser, but is not aggressive enough on its own. A colored glass filter (IR-80,
passband >760 nm) is inserted between the CGA830 and PMT to provide a high absorbance ofany scattered light within its stop band while avoiding the refluorescence of UV light.
The last approach to deal with scattered light, spatial filtering, is typically done by carefully
imaging the detection target onto the PMT, while rejecting light from other areas with the helpof a pinhole. Since the light pipes of the ion trap are non-imaging, the pinhole technique does notwork. Nevertheless, given the fact that a significant fraction of scattered light arises from lasers(UV, 769 nm) passing through the entrance and exit Brewster windows of the ion trap chamber,we can reduce the scattered light off of these windows with the following methods:(1) Setting the polarization of the lasers to be p-polarized relative to the Brewster windoworientation (i.e. horizontal polarization). In fact, since the fluorescence collection optics are
positioned above and below the ions, the fluorescence signal is maximized for a horizontally
polarized excitation laser.

90(2) Using Suprasil, a fused silica material with low bubble content, in place of regular quartz
or fused silica for the Brewster windows.
(3) Extending the distance between the ion trap and each Brewster window.
(4) Inserting baffles between the ion trap and each Brewster window (Fig. 5.2d). The baffles aremachined out of stainless steel to a conical razor blade tip and painted with Ball Aerospace
Flat Black paint. The razor blade tip limits the extent of diffraction fringes that may result
if the laser beams are clipped and diffracted by the baffles. The diameter of the baffles
opening, 14 mm, is chosen to be a compromise between not clipping the laser beams versus
decreasing the probability of scattered light off the windows making its way into the ion
trap chamber.
The above techniques of suppressing scattered light also tends to deteriorate the signal collection efficiency a little. Most notably, time gating and wavelength filtering reduces the fluorescencephoton collection efficiency by 0.7 and 0.6, respectively. According to the collection efficiency budget outlined in Table 5.1, with ∼500 ions in a single rovibronic level, the total number of photons
detected by a single PMT is estimated to be only 0.8 per shot, where the loss in efficiency is mostly
dominated by the PMT quantum efficiency. Nevertheless, the combination of all three scattered
light suppression techniques brought the scattered counts down to 0.1 photon per shot.

5.2

LIF signal
With the estimated signal-to-noise ratio optimized, we proceeded to detect the states of thetrapped HfF+ ions using LIF. Fig. 5.3a shows a LIF spectrum of ions that have been trapped for
2 ms, recorded by scanning the frequency of the 769 nm laser centered on the Q(1) rotational line.
The LIF signal is on the same order of magnitude as that estimated, i.e. 0.4 photons per shot.
The rotational line has a full width half maximum of 240(24) MHz, which is dominated by the RF
micromotion-induced Doppler effect of the trapped ions. In order to detect a LIF signal beyond
2 ms of trapping time, we needed to install a home-built fast shutter [53, 78] to block the weak

91

0.6

0o
o

20

0.4

o

40

0.2

{

0

Time

750

800
Wavelength (nm)

CGA830(c ) 1
Transmission

PMT turns on

150ns

FB820

(b)

769 nmlaser fires

Transmission

(a)

850

0o

0.8

o

20
0.6

o

40

0.4
0.2
0

700

750 800 850
Wavelength (nm)

900

(d)

Figure 5.2: (a) Time gating of the PMT to reduce the detection of scattered light from the 769 nm
excitation laser. (b) Plots of the bandpass filter FB820 transmission versus wavelength for different
angles of incidence. (c) Plots of the colored glass alternative long-pass dichroic filter CGA830
transmission versus wavelength for different angles of incidence. In both (b) and (c), the gray dashedlines denote the excitation laser wavelength at 769 nm, at which scattered light is the strongest andneeds to be suppressed most aggressively. The dotted black lines denote the fluorescence wavelength
at 818 nm, at which the filters need to have high transmission for efficient fluorescence collection.
(d) Photograph of a light baffle, which is placed in between the ion trap and Brewster window to
reduce scattered light.

92
Table 5.1: Effects of various components of the fluorescence collection experiment on the collection
efficiency.
Total number of trapped ions
Fraction of ions in 1 Σ+ , ν ′′ = 0, J = 1
Saturation
Franck-Condon overlap 1 Π1 , ν ′ = 0|1 Σ+ , ν = 1
Spatial overlap of lasers, ions and imaging axis
Detection solid angle for 1 cm ion cloudReflectivity of gold mirrors
Tranmission of filters and vacuum flange window
Signal remaining after time gating
PMT efficiency at 818 nm
Total photons per shot on both PMTs

800
0.6
0.5
0.3
∼ 1 (optimistic!)
0.6
0.85
0.6
0.7
0.05
0.75

continuous-wave component of 769 nm light whenever the 769 nm dye cell amplified pulse was not
firing, otherwise the continuous-wave component of the light (coming from the seed diode laser,transmitted through the dye cell) would pump away ions on resonance and serve as a source of LIF
signal decay. Fig. 5.3b shows the LIF signal measured as a function of the trap duration with the
shutter in place. There is an initial decay of the HfF+ LIF signal over the first few milliseconds,
after which the LIF signal remains constant over 40 ms. One clue to the source of initial LIF
signal decay comes from how the decay amplitude is less pronounced when the ions are squeezed
by ramping to tighter trap frequencies. Fig. 5.3c shows the LIF signal versus trap duration for a
HfF+ cloud that is 1.8 times smaller in area (along the radial directions x̂, ŷ) compared to that inFig. 5.3b. The LIF signal from 10–40 ms is correspondingly 1.9(4) times higher in Fig. 5.3c. It
seems, then, that the LIF signal collection at long times is simply limited by the initial expansionof the HfF+ ions in the trap, which reduces the spatial overlap between the HfF+ ions and theimaging axis formed by the light pipes.

5.3

Estimates for cavity-enhanced detection
Let us return to the fluorescence collection efficiency budget outlined in Table 5.1, and thinkof possible ways to improve it. One might look at the main culprit, the quantum efficiency of the

(a)

0.8

(b)

Photons per shot

0.7
0.6
0.5

(c)

0.4
0.3
0.2
0.1
−1000 −500

0

500

1000

Frequency (MHz) − c/769.102772 nm

Photons per shot Photons per shot93

f = 3 kHz : C = 0.24(3)

1

0.5

0

f = 6 kHz : C = 0.45(6)

1

0.5

0

0

10

20

30

40

50

Trap time (ms)Figure 5.3: (a) Frequency scan of the 1 Π1 ←1 Σ+ (0, 0) Q(1) transition, taken by performing LIF
on ions that have been trapped for 2 ms. (b) Plot of LIF signal as a function of trap duration fora 3 kHz trap. The signal is fit to a decaying exponential with offset C. (c) Plot of LIF signal as afunction of trap duration for a 6 kHz trap. The tighter trap in (c) yields a larger LIF signal C atlong times compared to the weaker trap in (b).

94
PMT, and exclaim, “Aha! Why don’t we use an avalanche photodiode instead, where the quantum
efficiency is much higher in the visible red or near infrared wavelengths?” The problem with theavalanche photodiode is its high dark count rate per square millimeter of active area (∼108 counts
per second compared to ∼100 counts per second for a PMT with the same active area). The darkcount rate can be reduced by shrinking the size of the active area, but unfortunately, for collecting
photons from a relatively diffuse cloud of ions, the signal is correspondingly compromised in a waythat reduces the signal-to-noise ratio. On the other hand, the output of a single-mode cavity may
be efficiently focused onto a small-area avalanche photodiode, thus it is worth considering cavityenhanced detection techniques. For the cavity-enhanced techniques presented in this section, we
refer the reader to References [84] and [95] for detailed explanations, and use the results from those
two Vuletić-group papers to estimate experimental parameters particular to our trapped HfF+ ions.
Cavity-enhanced techniques may be applied to either fluorescence or absorption for detecting
the states of HfF+ . In both cases, the coupling between the cavity and a single molecular ion canbe described by the cooperativity η, which is related to the ion-cavity coupling g, cavity decay
linewidth κ and ion spontaneous decay linewidth Γ by
η = 4g2 /(κΓ) .

(5.1)

In terms of experimental parameters like the cavity finesse F, cavity mode waist wc and scatteringcross section σs , we get the expression for η to be
η=

4σs F
.
π 2 wc2(5.2)

For cavity-enhanced fluorescence, the ratio with which a molecular ion emits fluorescencephotons into the cavity compared to that into free space is given by η. The ion number resolution∆N one can hope to achieve with fluorescence from N ions is [84]
s
2N
∆N =
,
qηp

(5.3)

where q is the photodiode quantum efficiency and p = 1 is the number of photons scattered permolecular ion. On the other hand, for cavity-enhanced absorption, the ion number resolution is95[84, 95]
∆N =

r

1
.
2qηp

(5.4)

Comparing between Eqs. (5.3) and (5.4), cavity-enhanced absorption has the potential for muchhigher ion number resolution.
It is worth noting that there are a number of different cavity-enhanced absorption techniques,
such as noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICEOHMS)[93], where the molecular ions are modulated at a frequency that is the same as the free spectral
range of the cavity. This section follows the particular experiment described in [95], where theRb atoms are only modulated at a small fraction (≈ 1/44) of the cavity free spectral range. The
frequency modulation of the Rb atoms is performed so as to place the first order red sideband nearor on resonance with the cavity, and then the cavity reflection of that sideband is heterodynedagainst the carrier. The shift in cavity resonance, which shows up as a shift in the dispersivelineshape, is then proportional to the number of ions coupled to the cavity.
Suppose, then, that we are interested in using cavity-enhanced absorption to resolve up to∆N ≤ 10 ions. For a sample of 50 ions in a single rovibronic state, a signal-to-noise ratio ≥ 5
offered by cavity absorption can only be achieved with competing spin readout methods if the total
detection efficiency is as high as 50%. To achieve ∆N ≤ 10 with a reasonable photodiode quantum
efficiency of q = 0.5, Eq. (5.4) dictates that η > 0.01. We now examine more closely the expressionfor η in Eq. (5.2) and estimate reasonable parameters needed to achieve η > 0.01.
For atoms that can be well approximated as a two-level system due to the use of a cycling transition, the scattering cross section is σsatom = 3λ2 /(2π). For molecules without cycling transitions,the scattering cross section is reduced from σsatom by the Franck-Condon overlap and electronic
and rotational state branching ratios. Of the HfF+ states lying below 22000 cm−1 with transitions
to 3 ∆1 , the 3 Π0− states (at ≈10400 cm−1 and ≈19200 cm−1 ) and 3 Σ0− state (at ≈21700 cm−1 )decay only to the 3 ∆1 state [86]; of these, the [10.4]3 Π0− ←3 ∆1 (ν ′ = 0, ν ′′ = 0) transition has themost favorable Franck-Condon overlap, as shown in Table 5.2. Including the rotational branching

96
ratio of the |J ′ = 0, Ω′ = 0, F ′ = 1/2i ← |J ′′ = 1, Ω′′ = 1, F ′ = 3/2i transition, the best scatteringcross section we can achieve is then σs = 0.52 × 0.5 σsatom = 0.26 σsatom . So far, we have not
yet taken into account the Doppler width of the ions. With a typical Doppler width of Γdopp =30 MHz along the axial direction, the scattering cross section is diluted down by Γ/Γdopp ∼ 104 ,i.e. σs = 2.6 × 10−5 σsatom .
Table 5.2: Franck-Condon overlaps | hν ′′ = 0|ν ′ i |2 between the 3 ∆1 , ν ′′ = 0 state and excited states[10.4]3 Π0− , [19.2]3 Π0− and [21.7]3 Σ0− of various vibrational levels ν ′ . The notation for the excitedelectronic states follows the same convention as that used in Chapter 2.
ν′[10.4]3 Π0−[19.2]3 Π0−[21.7]3 Σ0−

0
0.52
0.30
0.31

1
0.36
0.07
0.04

2
0.11
0.04
0.08

3
< 0.010.21
0.26

4< 0.010.22
0.21

5< 0.010.12
0.08

6< 0.010.04
0.02

Given the above scattering cross section, the remaining parameters we can choose to fulfil
η > 0.01 are the cavity finesse and mode waist: the lower the finesse desired, the smaller the mode
waist needed. The cavity mode waist is limited by the number of ions we can squeeze radially inthe trap. With the eEDM linear Paul trap presented in this thesis, the highest trap frequency we
can obtain in the radial direction is (2π)28 kHz, which comes from applying |Vrf | = 200 V andωrf = (2π)60 kHz. (Increasing ωrf does not help because we are limited by Vrf .) Using the typical
trap radius of 2 mm for a (2π)4 kHz trap, we can only get a radius of 0.76 mm with the squeezed
trap. Alternatively, we can run the eEDM ion trap as a cylindrical Paul trap, i.e. |Vrf | cos(ωrf t)
is applied to all six radial fins and a weak DC cylindrical quadrupole field that further confines
the ions radially is generated by the end cap electrodes. The cylindrical Paul trap does not offer
a higher trap frequency (maximum achievable ω = (2π)24 kHz) because the end cap electrodes inthe existing design are spaced too far apart. With the cavity mode waist limited to 0.76 mm, we
require, for a resolution of ∆N ≤ 10 ions, that the cavity finesse be F ≥ 1010 .
State-of-the-art cavities have finesses in the range of 105 − 106 and are dominated by losses
in the cavity mirrors [92]. The required cavity finesse of 1010 , then, is quite impossible. The main

97
limitation is the small scattering cross section due to the ion cloud’s large Doppler widths. With
these challenges in mind, we retired the idea of implementing cavity-enhanced absorption. We mayrevisit it as a spin-readout technique to be used with future generations of eEDM experiments
where the molecular ions may be sympathetically cooled to much lower temperatures and where
the ion trap geometry is more compact.

Chapter 6
Spin readout techniques (II): photodissociation

In the previous chapter, we saw how we could detect the state of HfF+ ions in the 1 Σ+ (ν ′′ = 0)
level using laser-induced fluorescence. A possible path from there to the eEDM measurement is
to extend the capability of LIF to 3 ∆1 (ν ′′ = 0) state detection, where a known transition to the3 Φ (ν ′ = 1) level can be excited by a 684 nm laser, and fluorescence down to the 3 ∆ , ν = 2 level at
21

763 nm can be measured and reasonably well-filtered from the excitation wavelength [16]. However,as shown in Table 5.1, the LIF efficiency can be easily nickled-and-dimed down to a paltry 0.18%
for a single PMT, and the dominant limitation in efficiency — the quantum efficiency of the PMT
at 763 nm — remains as miserly as 8%. Given these numbers, even if we were to optimistically
populate 30 HfF+ ions in a given |F, mF , J, Ωi state of the 3 ∆1 , ν ′′ = 0 manifold, our readout signal
would only be 0.05 photons per shot. With a repetition rate of 4 Hz (limited by the pumping speed
in the ablation/source chamber to remove residual gas after the pulsed valve fires, also assuming a
coherence time of 0.25 s), such a low readout signal would mean as long as 2.5 hours spent to reach1 × 10−27 e cm.
Counting photons from non-cycling transitions in a diffuse cloud of molecular ions is hard.
Counting ions, on the other hand, is relatively easy: the quantum efficiency of detection for ahighly energetic (> 2 keV) ion hitting a single MCP channel can be on the order of unity. The
overall efficiency of the ion detector is then limited by the open area ratio (ratio of active channel
area to the total MCP area) and by the transparency of the ground mesh above the MCP toapproximately 25%. In all the experiments discussed so far, HfF+ ions have been counted using

99
the MCP in a manner indiscriminate for the ions’ internal state. To be sensitive to the state of
HfF+ , one can use a laser to resonantly excite HfF+ molecules to a repulsive potential, which breaks
apart the molecules into Hf+ and F. The Hf+ atomic ions can then be counted on a MCP. Usingsuch a resonance-enhanced multi-photon dissociation (REMPD) scheme, the detection efficiency
is potentially much higher than that for LIF: if it were higher, say, by a factor of 10, the eEDM
measurement could be carried out 10 times faster to reach the same statistical sensitivity (assuming
the same level of noise). To quote Eric’s famous motivational refrain, this would ideally translate
to “less time spent taking data, more time spent skiing”.
Performing REMPD, alas, is easier said than done. Firstly, we have to find the repulsive
curves, which are likely to lie > 50000 cm−1 . Secondly, photodissociating in a rotational state
specific way means that we also have to find intermediate bound states of energy < 40000 cm−1 , sothat we can drive a bound state-bound state transition with a weak but narrow UV/visible laser
before hitting the repulsive curve. A simultaneous search for (at least) two unknown potential
curves is non-trivial, especially since theoretical calculations on HfF+ have only been performed up
to 22000 cm−1 . This chapter presents the following: the basics of photodissociation; the experiment
sequence and layout needed to prepare for a survey scan of high-lying HfF+ states; spectroscopyof HfF+ states at > 30000cm−1 ; our preliminary understanding of the repulsive curve; the experimental efficiency of photodissociation as a state readout method.

6.1

Basics of photodissociation

6.1.1

Direct photodissociation

In direct photodissociation, a HfF+ molecule is excited by a laser (or multiple lasers) to amolecular potential that is purely repulsive in nature, before breaking apart into its constituent
atoms:
HfF+ + hν → Hf+ + F .

(6.1)

100
Repulsive molecular potentials lie above the bond dissociation energy D0 , which is the minimum
energy necessary to break apart a molecule starting in its ground rovibronic state. D0 has been
estimated from ab-initio calculations to be 51400(300) cm−1 [62]. As shown in Fig. 6.1a, D0 can
also be estimated from the measured bond dissociation energy of neutral HfF (55600 ± 1600 cm−1[6]) and the ionization energies of HfF and Hf (59462 cm−1 and 55048 cm−1 , respectively) [4, 12]
to be 51200 ± 1600 cm−1 :D0 (HfF+ ) = D0 (HfF) + IE(Hf) − IE(HfF) .

(6.2)

If the repulsive molecular potential arises from constituent atomic orbitals that are in their groundconfigurations (i.e. Hf+ (2 D3/2 ) + F(2 P3/2 )), the potential energy at large internuclear separation,
DR→∞ , asymptotes towards the bond dissociation energy (Fig. 6.1b). Conversely, if the repulsive
potential is the result of anti-bonding between excited atomic orbitals, DR→∞ is higher than D0(Fig. 6.1c).
The excitation of molecules to the repulsive potential takes place quickly compared to the
motion of the constituent atomic nuclei, i.e. where the Born-Oppenheimer approximation is valid.
The energy of the molecules at the point of excitation on the repulsive curve (U ∗ ) that is in excess
of DR→∞ gets released as the kinetic energy of the dissociation products. For Hf+ and F, thelighter fluorine atom flies away with 10 times as much kinetic energy compared to the Hf+ ion.
When the trap is dumped onto the MCP, the Hf+ ion, being 10% lighter than HfF+ , is separated
from any residual HfF+ molecular ions in time-of-flight and detected on a MCP.
To figure out the position and width of the photodissociation resonance, we can use thereflection approximation [48, 35]: the repulsive potential in the vicinity of U ∗ , where U ∗ is many
vibrational energies above DR→∞ , can be approximated as a linear negative slope. For such highlying vibrational levels, the vibrational wavefunction amplitudes are mostly concentrated at the
wavefunction turning points, i.e. at the internuclear separation where the repulsive slope lies (seeFig. 6.1d). The Franck-Condon overlap between these high-lying dissociative vibrational states andthe lower vibrational state gives the probability of dissociation for a given laser frequency. Therefore,101
over the range of frequencies connecting the lower state to the repulsive slope, the photodissociation
resonance looks like the wavefunction of the lower state reflected about the negative linear slope ofthe repulsive potential.
As mentioned previously, there are no theoretical calculations describing HfF+ molecularpotentials lying above 22000 cm−1 , and certainly none above the bond dissociation energy. Nevertheless, it has been estimated, by extrapolating from the calculated molecular potential of PtH+
[54], that a 3 Σ repulsive potential of slope 80000 cm−1 /Å lies at 71000 cm−1 [83]. It is forbidden to
make a transition directly from the ground 1 Σ+ state to a 3 Σ state, so one would need to go throughan intermediate mixed-spin state. The photodissociation transition to the 3 Σ state is estimated tohave a resonance of width 4200 cm−1 and cross section 3.8 × 10−19 cm−2 (assuming an electronictransition dipole moment of 0.3 ea0 ), which requires a 266 nm laser pulse of energy ≈250 mJ tosaturate an ion cloud of 2 mm radius.

6.1.2

Predissociation

A 10 ns laser pulse at 266 nm with a few hundred mJ of energy demands a rather hefty
Nd:YAG laser for its source. In order to use less pulse energy for photodissociation, one canuse predissociating molecular states. In pre-dissociation, the molecule is excited to a bound-state
molecular potential that has an avoided crossing with a repulsive potential (see Fig. 6.2) [48, 35]:
HfF+ + hν → HfF+(∗) → Hf+ + F .

(6.3)

Comparing between predissociation and direct dissociation is analogous to comparing between autoionization and direct photoionization. Since the oscillator strength for a bound-bound transition
tends to be stronger than for a bound-free transition, the laser pulse energy required to access apredissociating/autoionizing state tends to be smaller compared to that for its direct analog. The
predissociation/autoionization resonances are also generally narrower, which means that they are
harder to find! For predissociation, the reflection approximation does not hold because of structurein the upper bound-repulsive potential. In fact, sometimes the point of avoided crossing may occur

102

(a)

(b)

(c)

+

Hf + F
D0(HfF+)
IE(Hf)
IE(HfF)

Hf
DR

+(*)

+F

8

+

EnergyEnergy1

Energy

XS
+
HfF

+

Hf + F

Hf + F

HfF
R+

D0(HfF+)8

D0(HfF+)=DR2

HfF

Hf + FU*

D0(HfF)X D3/2

+

U*

HfF
R

+

R

(d)

Figure 6.1: (a) Schematic of ground state molecular potentials for both neutral and ionic HfF,
illustrating how to derive the bond dissociation energy of the HfF+ molecular ion species from theionization energies and bond dissociation energy of the neutral molecule species. (b) Schematic ofground and repulsive molecular potentials in HfF+ , where both molecular potentials come from Hf+
and F atomic orbitals in their ground state configuration, such that the repulsive potential at large
internuclear distances DR→∞ tends to the bond dissociation energy D0 . U ∗ is the energy neededto access the repulsive potential from the ground state. (c) Schematic of ground and repulsive
molecular potentials in HfF+ , where the repulsive potential is composed of atomic orbitals inan excited state configuration, i.e. DR→∞ > D0 . (d) Using the reflection approximation, thedissociation resonance (vertical Gaussian) is a reflection of the lower state’s wavefunction (thinline) about the repulsive potential that has been approximated as a linear negative slope, as shownin the depicted example for Cl2 [35].

103such that U ∗ is barely above DR→∞ , which means that the constituent atoms fly off with a much

Energylower kinetic energy, simplifying their detection.

HfF

+(*)

Hf+ + FR
Figure 6.2: The avoided crossing of a bound state (blue dashed line) and repulsive state (red dashedline) gives rise to a predissociating potential (black line) and a more tightly confined bound state(purple line).

6.2

Practical challenges and considerations

6.2.1

HfF+ creation

For photodissociation to work as a state detection method on the eEDM experiment, thequestion is not so much the nature of the molecular potential at > 50000 cm−1 , but where we needto tune our lasers to hit a repulsive/predissociating state. The best tunable laser at our disposal for
performing a survey spectroscopy of HfF+ lines — a SIRAH Precision Scan pulsed dye laser and its
motorized doubling crystal setup — was already being used to deliver the second photon at 368 nm
for photoionizing HfF. Since we did not know how likely we were to succeed in performing photodissociation, we were reluctant to buy another pulsed dye laser system specially for photodissociation.
Instead, we freed up our existing pulsed dye laser by using 308 nm (unchanged from before) +104
355 nm (the third harmonic of a Nd:YAG laser) to excite neutral HfF to the autoionizing Rydberg
state. Since the total energy of a 308 nm and a 355 nm photon lies above the ionization thresholdfor the ionic 3 ∆1 state, this autoionization scheme meant that the HfF+ ions could be formed in
the 1 Σ+ (ν = 0), 1 Σ+ (ν = 1) and 3 ∆1 (ν = 0) states, which would dilute the number of ions in
any given quantum state and possibly reduce our chances of seeing a photodissociation signal froma particular state. We attempted to circumvent the problem of initial state dilution by searchingfor a different intermediate state in neutral HfF that could be addressed using 312–320 nm light,
so that when combined with the second photon at 355 nm, would only allow the creation of 1 Σ+ions. Unfortunately, most of the transitions identified in the target wavelength range originatedfrom the ν = 1 vibrational level of the X 2 ∆3/2 state in neutral HfF, which meant that the twophoton Rydberg autoionizing states still lie above multiple ionization thresholds. Thus, we stuck
to the autoionization scheme with the 308 nm and 355 nm lasers. In retrospect, and as shown in
Section 6.3, having the additional HfF+ population in three different vibronic states turned out tobe a useful feature in understanding photodissociation spectroscopy!

6.2.2

Lasers, lasers and more lasers

As outlined at the start of this chapter, there is a need to search for HfF+ states in two
frequency regions: repulsive/predissociating states above 50000 cm−1 and bound states below
40000 cm−1 . To avoid performing a two-dimensional search for states, we needed to increase
our chances of successfully accessing multiple molecular states by shining as many lasers as possible onto the ions. The lasers we had at our disposal were the following: the fundamental andsecond harmonic light from the SIRAH Precision Scan tunable dye laser, all four harmonics of
the Nd:YAG laser (1064 nm, 532 nm, 355 nm, 266 nm), 308 nm and 769 nm (previously used for
LIF). Overlapping 8 laser beams, most of which possess pulse energies of ∼ 1 mJ, over such a wide
range of wavelengths turned out to be a non-trivial task. Fig. 6.3 shows a layout of the optics used
to combine all 8 laser beams using dichroic mirrors, for the particular case where the wavelength
range of the Precision Scan dye laser in the fundamental was 547–581 nm (using Pyrromethene 580

105dissolved in ethanol as the dye gain medium). Dichroic mirrors (see Table 6.1) instead of beam
splitters were preferred in the optical setup so as to minimize loss of laser pulse energy. Since thelaser beams are propagating collinearly through the vacuum chamber, the successful attainment ofa LIF signal meant that the lasers are overlapped with the trapped ions.
Since the Nd:YAG laser used to generate 355 nm light and pulse-amplify 308 nm light forphotoionization was also used to pump the tunable pulsed dye laser, the lasers used for photoionization and photodissociation fired at the same time. Care had to be taken to match the lasers’
path lengths so that the laser beams are temporally overlapped when they traverse the ion cloud.
The presence of the photodissociation lasers at the time of photoionization, however, is unwelcome:two-photon ionization from 266 nm, for instance, could dominate the ionization process so muchthat the HfF+ ions could be formed with initial population spread across an even larger numberof vibronic states. Shutters were therefore used to gate out any laser other than the 308 nm and355 nm lasers during photoionization. Given the 10 Hz repetition rate of the Nd:YAG laser, thephotodissociation is then carried out only after the ions have been trapped for 100 ms.
Table 6.1: Specifications of dichroic and broadband mirrors used to overlap laser beams of different
wavelengths for photodissociation.
Optic
MPQ-245-390
LWP-45-Rp-266-Tp-308
LWP-45-Rp-300-Tp-355
LWP-45-Rp-355-Tp-515
LWP-45-Rp-532-Tp-607
SWP-45-Rp-780-Tp-633
BBDS
BSR31
BSR15
DMLP567
DMLP900

Reflected
λ (nm)
245–390258–274
291–309345–365
516–548757-803
350–1100355
1064
380–550, 532, 1064
400–872

Transmitted
λ (nm)
>308
>355
>515
>607
600–685532/1064532
584–700
932–1300

DamageThreshold
0.92 J/cm2 , 10 ns at 532 nm
10 J/cm2 , 20 ns, 20 Hz
10 J/cm2 , 20 ns, 20 Hz
10 J/cm2 , 20 ns, 20 Hz
10 J/cm2 , 20 ns, 20 Hz
10 J/cm2 , 20 ns, 20 Hz
1 J/cm2 at 355 nm
4 J/cm2 , 20 ns, 20 Hz
10 J/cm2 , 20 ns, 20 Hz
2 J/cm2
1.21 J/cm2 at 532 nm

106

MPQ-245-390

769nm

MPQ-245-390
Y1

50/50 BS

PS611

1064nm

308nm
PS611

Pellin Broca
Prism

E03

E03
PBSO532

BSR31

Pyrromethene 580
547-581nm

PS611

355nm

532nm

BSR15
266nm

Y3

LWP-45-Rp-355-Tp-515

70T/30R BS
MPQ-245-390
Pyrromethene 580, doubled
273.5-290.5nm

MPQ-245-390
1064nm, 532nm, 355nm

LWP-45-Rp-266-Tp-308
LWP-45-Rp-300-Tp-355

PS611
BBDS

Figure 6.3: Layout of optics used to overlap 8 laser beams (wavelengths in italics) in a search forphotodissociation transitions. Table 6.1 gives a list of specifications for most of the optics shown.

107
6.2.3

Hf+ detection

For photodissociation to occur, the combination of laser frequencies needs to be higher thanthe bond dissociation energy. On the other hand, if too high a dissociation potential is accessed,
the dissociation products (notably Hf+ ) can fly away with a kinetic energy so large and in such anear-isotropic manner, that the detection efficiency on a MCP located along a given direction isdiminished. The MCP detection can be improved by using the trap electrodes to give the ions a
big velocity ‘kick’ vkick,x towards the MCP — big enough to overwhelm the velocity vP D inheritedfrom photodissociation. The angle subtended by the two velocities should be smaller than theangle subtended by the MCP (9 mm radius of active area, 11.6 cm from the ion trap center) (seeFig. 6.4a):where

vP D,y≤vkick,x1
mHf vP2 D,x + vP2 D,y + vP2 D,z =2

0.9= 0.08 ,11.6
1
3
mHf vP2 D =(U ∗ − DR→∞ ) .
2
10

(6.4)
(6.5)

For a ‘kick’ velocity of 5500 m/s, Eqs. (6.4) and (6.5) predict that we can access dissociation
potentials as high as 41000 cm−1 above DR→∞ .
A higher ‘kick’ velocity not only increases the range of energies over which we can detect
dissociation potential curves, but also tends to increase the mass resolution between the dissociated
Hf+ ions and the remaining HfF+ ions, both of which get ejected at the same time. This is because
a higher ‘kick’ velocity maps the HfF+ ion cloud width onto a narrower distribution in arrival time(see Fig. 6.4b), and the well separated ion peaks provide a good level of discrimination between
any dissociated Hf+ signal ions and the tail of the HfF+ distribution.
Besides ions from the HfF+ distribution contaminating the Hf+ signal, the photodissociation
signal to noise ratio can be reduced due to two sources of background: 1. the photodissociation lasers
can ionize residual background gases to give ions that show up at all times on the MCP, including
the time window corresponding to the Hf+ signal; 2. the photoionization lasers can off-resonantly
ionize Hf to give Hf+ (henceforth referred to as “aboriginal” Hf+ ), which remains trapped for theentire duration until the photodissociation lasers fire. To remove the background ions created by

108
the photodissociation lasers, we can trap any dissociated Hf+ ions for a short time before ejecting
the ion cloud onto the MCP, thereby separating the dissociation signal in time from the promptly
ionized gases. Specifically, the additional post-dissociation trap duration Ttrap should be chosen sothat the energetic Hf+ ions can be focused onto the MCP over their flight time to the detector Tdet
(Fig. 6.4c). For ions in a trap of secular frequency ω and oscillation amplitude y0 , the focusing
condition is expressed as a zero net displacement in the transverse direction ŷ:y + ẏTdet = y0 sin(ωTtrap ) + ωy0 Tdet cos(ωTtrap ) = 0 ,tan(ωTtrap ) = −ωTdet ,Ttrap =

1
− tan−1 (ωTdet ) + π .
ω

(6.6)

While typical trap frequencies lie in the range of (2π)3–6 kHz, the trap frequencies in all three
directions are ramped up to the same value of (2π)13 kHz just before photodissociation, so as tosqueeze the ion cloud and allow for better spatial overlap with the dissociation laser beams. For
Tdet = 21 µs and ω = (2π)13 kHz, the post-dissociation trap wait time according to Eq. (6.6) isthen Ttrap = 0.026 ms. Since the ions can be ejected from the trap only after an integer number oftrap RF cycles to avoid imaging the RF micromotion velocity, Ttrap is chosen to be a multiple of
the refocusing time 0.026 ms and (2π)/ωrf , which, in the case of ωrf = (2π)50 kHz, ends up giving
Ttrap = 0.1 ms.
To reduce the aboriginal Hf+ ions created by the photoionization lasers (in particular,
355 nm), one can operate the ion trap in a regime that is stable for HfF+ but unstable for Hf+ up
to the time of dissociation. Alternative to ramping the trap to a different set of {a, q} parameters,
we can ‘kick’ the ion cloud twice (along x̂) during the trap cycle to ‘hide’ the promptly created Hf+ions under the HfF+ distribution when the ion cloud is ejected after dissociation (see Fig. 6.5). The
first ‘kick’ sets both HfF+ and Hf+ ions sloshing in the trap at frequencies differing by 10% (fora ≪ q, the trap frequency is approximately proportional to q and therefore inversely proportional tothe ion mass). After some time Thide , the two ion species dephase in their slosh motion such that asecond ‘kick’ removes (adds to) the momentum imparted by the first ‘kick’ for the HfF+ (Hf+ ) ions.

109

(a)

(b)

vkick

vPD, y+Hf

y5850 m/s

x4470 m/s

W

Ions

11.6 cm(c)+3090 m/s

Hf
trajectoryvkick, x1720 m/s‘Fast’
MCP
f 1.8 cm

20

40

60

80

‘Fast’
MCP

Arrival time (ms)Figure 6.4: (a) To be fully captured by the MCP detector (subtending a solid angle Ω from theion cloud), the Hf+ ions need to be ejected towards the MCP with a longitudinal velocity vkick,xthat is large compared to their transverse velocity vP D,y . (b) Arrival time of Hf+ (red) and HfF+
(blue) ions on the ‘fast’ MCP: the faster the ejection velocity vkick , the shorter the arrival time andthe better resolved the two ion species. This data is taken by simulating the presence of Hf+ and
HfF+ ions in the trap by ionizing both neutral Hf atoms and HfF molecules. (c) Trajectory of the
Hf+ ion cloud when ejected from the trap after a refocusing time Ttrap , so that the Hf+ ions arefocused onto the MCP.

110
The HfF+ ion cloud subsequently becomes stationary while the Hf+ ions’ center-of-mass slosheswith an even greater amplitude, until the trapped ions are ejected at Ttrap after photodissociation,
at which time the Hf+ ions should be initially moving along −x̂ and eventually catch up with thearrival of HfF+ on the MCP. Using the double ‘kick’ method, we reduced the background Hf+ ionsby a factor of 4. Nevertheless, the application of the double ‘kicks’ suffered from reproducibility
issues due to interference on the ion trap voltages from nearby laser shutters, so we eventually
discarded the procedure and lived with the small amount of aboriginal Hf+ background.

6.3

Photodissociation spectroscopy of HfF+

6.3.1

An initial disappointment

When we first begun to look for photodissociation lines, the 10 mJ 266 nm laser immediately
started photoionizing the background gas to give 2–5 ‘Hf+ ’ ions per shot. The photodissociation
signal-to-noise ratio would have been only 0.1 if our initial photodissociation efficiency was 1%.
Thus, we temporarily removed the 266 nm laser from the photodissociation sequence and scanned
through the wavelength range afforded by using Pyridine 2 in the tunable pulsed dye laser (691–751 nm in the fundamental). This dye, in combination with the other fixed wavelength lasers, would
allow us to access a sum frequency range of 49000–58000 cm−1 if using a two-photon transition and
67000–77000 cm−1 with a three-photon transition. This scan yielded no photodissociation signal,
which was somewhat discouraging.
Given that the HfF+ bond dissociation energy was ≈ 52000 cm−1 , we would have been hoping
to hit either a predissociating state below 60000 cm−1 with two on-resonant photons or a predissociating/repulsive state above 60000 cm−1 with three on-resonant photons. Both situations required
us to be at least ‘doubly lucky’. On the other hand, if we were able to employ the 266 nm laser, we
could access states above 60000 cm−1 with two photons, and if the predissociating/repulsive state
there was broad enough, we could potentially access it even if one of the two photons was at a fixedwavelength! It was therefore necessary to solve the problem of background ionization by 266 nm,

111

(a)

T=t0+thide

T=t0

T=tphotodissociate

+

HfF
+

Hf

‘Fast’ MCP(b)Electric
field ‘kick’ 1

Electric
field ‘kick’ 2

Eject ionsfrom trap

Ions

1.5
No kicks
2 kicks to hide Hf+

+

1

Hf

HfF+

0.5
0
28

29

30

31

32

33

34

HfF+, Hf+
35

36

37

38

39

Arrival time (ms)Figure 6.5: Hiding aboriginal Hf+ ions. (a) A pair of velocity ‘kicks’ is applied to the ions at times
t0 and t0 + thide , which are chosen such that the Hf+ and HfF+ ions are moving in phase and out ofphase relative to each other, respectively. In this way, the HfF+ ions remain stationary whereas the
Hf+ ions oscillate with an even larger velocity after the second ‘kick’. When the photodissociation
lasers fire, the Hf+ ions should be moving away from the detector, so that they eventually arrive
the MCP at the same time as the heavier HfF+ ions. (b) Two oscilloscope traces depicting thearrival of Hf+ and HfF+ with (red) and without (blue) the pair of ‘kicks’. Without the ‘kicks’, thebump at earlier (later) time indicates the arrival of Hf+ (HfF+ ). With the ‘kicks’, both ion species
arrive at the same time. This data is recorded with the Hf+ and HfF+ ions created by ionizing
both neutral Hf atoms and HfF molecules.

112
so that we could include the 266 nm laser without hurting our signal to noise ratio.
Ions produced by the 266 nm laser turned out to obey the following characteristics: 1.
they were produced regardless of whether HfF neutral molecules were being created in the sourcechamber; 2. they could be trapped for several hundred milliseconds; 3. when ejected onto the‘fast’ MCP, their arrival time was 30 times broader than the arrival time window of the Hf+ ions,corresponding either to a wide range of masses or a very diffuse cloud of trapped ions. Based onthese observations, we concluded that the ions came from background gases introduced into thevacuum chamber during the trap assembly (also affectionately termed “isogreasanol”), and could
be decreased by baking the vacuum chamber. Indeed, after baking the ion trap setup to 200◦ overtwo days, the background ionized gas decreased by an order of magnitude, and we were poised toretackle photodissociation.

6.3.2

HfF+ lines galore!

To increase the chances of accessing high-lying dissociative states with two on-resonant photons, we changed the gain medium for the tunable pulsed dye laser to Pyrromethene 580 (fundamental wavelength range 547–581 nm). This allowed us to access frequencies as high as 6900074000 cm−1 with either two tunable 34500–37000 cm−1 photons (for 1+1 REMPD) or a tunable
31400–36400 cm−1 photon and a fixed 37600 cm−1 (266 nm) photon (for 1+1’ REMPD). To ourpleasant surprise, we found several HfF+ transitions in the frequency range 32500–36500 cm−1 ,made by a UV photon from the frequency-doubled output of the tunable dye laser. The fact that
we can detect the HfF+ transitions by counting Hf+ indicates that we are hitting at least one dissociating state. The dissociating state(s) could be accessed by either the fixed 266 nm or a second
tunable (> 32900 cm−1 ) photon, which means that the state lies above 70500 cm−1 .
Fig. 6.6 shows a summary of the HfF+ transitions found in the vicinity of 35000 cm−1 ,scanned using both Pyrromethene 580 and Pyrromethene 597 as the gain medium of the tunable
dye laser. The gap in the spectrum is due to Wood’s anomaly, which is a grating configurationthat causes the dye laser to stop lasing in that wavelength region for a 1800 lines/mm grating.

113
Since many of the transitions at 35000 cm−1 come from two 32900–36500 cm−1 photons accessing
a dissociating state, the intensities of transitions shown in Fig. 6.6 reflect a convolution of boththe photodissociation resonance (which is almost surely not saturated by the second photon) andthe variation in gain of the tunable dye laser; in particular, the pulse energy is diminished in thevicinity of the Wood’s anomaly. The assignment of vibronic bands is aided by the initial populationof HfF+ ions in three different vibronic states: using the known spacing between the three initialvibronic states [16], we can identify transitions between the same upper state at > 30000 cm−1and one of the three lower vibronic states, as indicated by the line markers in Fig. 6.6. Some of
the isolated transitions that remain unidentified may come from upper states that have allowed

Hf+transitions only to either the 1 Σ+ or 3 ∆1 state, but not both.

−2500

−2000

−1500

−1000

−500

0
−1

500

1000

1500

−1

First photon frequency (cm ) − 35000 cm

Figure 6.6: REMPD spectroscopy of HfF+ transitions at 32500–36500 cm−1 , detected by photodissociating HfF+ into Hf+ and F. The gap in the spectrum is due to Wood’s anomaly of the laser
grating that causes a loss in laser intensity. Transitions that have been identified as originating fromthe 1 Σ+ (ν ′′ = 0),1 Σ+ (ν ′′ = 1) and 3 ∆1 (ν ′′ = 0) lower states to excited states at > 30000 cm−1 aredenoted by red, green and blue vertical lines, respectively. Vertical lines connected by a horizontal
magenta line belong to transitions terminating on the same upper vibronic state.

To identify the individual rotational lines of a given vibronic band, we tried to reduce thepulse energy of the first photon (provided by the tunable dye laser) to avoid power broadening therotational lines. However, since the tunable dye laser was sometimes also responsible for providing
the second photon in photodissociation, a lower dye laser pulse energy also reduced the overall
photodissociation signal, making it more difficult to discern different rotational lines. Instead oflowering the dye laser pulse energy, a narrowband continuous wave laser at 13002 cm−1 tuned to114
resonance of one of the rotational lines in the 1 Π1 ←1 Σ+ (0, 0) transition was used to first opticallypump away ions from a given 1 Σ+ (ν ′′ = 0, J ′′ ) lower state before photodissociating the HfF+ ions.
The presence of the continuous wave laser would leave a depletion gap in the vibronic band at≈ 35000 cm−1 , which can in turn be identified as a rotational line of that band. Fig. 6.7 shows
the rotational lines identified using such depletion spectroscopy for a vibronic band at 35975 cm−1 .
The lower state rotational constant was fixed to be the known value for the 1 Σ+ (ν ′′ = 0) state,i.e. 0.305 cm−1 [16]. The upper state rotational constant was then identified to be 0.269 cm−1 , andthe lack of a Q branch indicated that the upper state has Ω′ = 0.

6.3.3

Nature of photodissociating state at 72000 cm−1

While having one tunable dye laser allowed us to perform REMPD spectroscopy of HfF+
intermediate states, a scan of HfF+ states above the bond dissociation energy could be carried out
only with two tunable lasers. Fig. 6.8a shows a spectrum of the dissociating states at 72000 cm−1 ,measured by tuning the first photon (70 µJ) to resonance with the vibronic band at 35976 cm−1 andthen scanning the second photon (≈1 mJ). Care was taken to tune the second photon off-resonancefrom transitions at 36000 cm−1 (see Fig. 6.8b) to avoid artificially enhancing the dissociation process
arising from the more intense second photon addressing multiple rotational levels. The plotted Hf+ions are taken to be the difference between chopping the first photon on versus off, to account for
any variations in the background ionization process with the second photon’s frequency. To oursurprise, there is structure in the dissociation resonance at 72000 cm−1 , which can indicate that:(1) the intermediate state at 36000 cm−1 is at a high-lying vibrational level, and is mapped
onto the dissociation resonance using the reflection approximation for a purely repulsive
curve, or(2) the dissociating state at 72000 cm−1 is a predissociating state whose structure comes fromone or more avoided crossings, or(3) some combination of the above reasons.

115

J"=4

Hf+ (with cw depletion)- Hf+ (without cw depletion)

Depleted
J"=3

J"=2

J"=1

J"=0

Hf+ (without
cw depletion)
Simulationof vibronic
band

-4

-2

0

2
-1

4

) - 35975 cm - 1

Figure 6.7: Depletion spectroscopy of the Ω′ = 0 ←1 Σ+ vibronic band at 35975 cm−1 (shown as
the unresolved, thick black line in the second lowest panel). To resolve the individual rotationallines, the vibronic band is scanned over in the presence of a depletion laser driving a particularrotational transition of the 1 Π1 ←1 Σ+ band, and the difference in Hf+ with and without the
depletion laser is plotted as the colored lines with error bars. The thin black line (bottom panel)denotes the simulated vibronic band with its R branch on the right (dot-dashed vertical lines) andP branch on the left (dashed vertical lines).

116
To truly understand the nature of the dissociating states, more spectroscopy work — specifically, more scans of the dissociation resonances and a better understanding of the intermediate
states at 35000 cm−1 — needs to be done. Nevertheless, the goal of preforming photodissociation
is not to understand the high-lying states of HfF+ , but to use dissociation as an efficient detection
tool for the states involved in the eEDM search. One way to efficiently carry out photodissociation
is to look for the dissociation resonance with the largest cross section, which involves a non-trivial
two-dimensional search for HfF+ states with two tunable lasers dedicated for dissociation. The
other method is to use the fourth harmonic of a Nd:YAG laser at 266 nm to access the second
dissociation transition. In the latter case, even if the dissociation cross section is small, we canmaximize the dissociation efficiency by saturating the second transition with higher pulse energy.
The latter scheme is much easier to implement than using two tunable lasers, and is hence employed
as the method of dissociation for the remainder of this thesis.

6.4

Photodissociation as a readout tool

6.4.1

Saturation of dissociation transition

Fig. 6.9 shows the saturation curve, which is a plot of photodissociation efficiency versus
pulse fluence, for the dissociation resonance accessed by saturating the Ω′ = 0 ←1 Σ+ transition
at 35975 cm−1 with the first photon and varying the pulse fluence F (i.e. pulse energy for a given
beam area) of 266 nm as the second photon. Each point on the saturation curve is taken to be thedifference in Hf+ ions counted with the first photon present versus absent, so as to remove the effects
of a more intense 266 nm pulse more efficiently ionizing the background gas. The saturation curves
were recorded for two different 266 nm beam waists. For the bigger beam waist (w0 = 5.0 mm),the saturation curve (open circles) is mostly linear. For the smaller beam waist (w0 = 3.3 mm), theHf+ counts (open triangles) clearly saturate above 50 mJ/cm2 but to a smaller value of ion counts,
due to laser overlap with a smaller fraction of the ion cloud. Each saturation curve is fit to a single
exponential A(1 − exp(−F/FS )), where FS is the saturation fluence. The single exponential is only

117

REMPD (1+1’) signal(1’−photon tunable)

(a)

−400

−200

0
−1

200

400
−1

Total energy (cm ) − 72000 cm

REMPD (1+1) signal

(b)

−200

−100

0

100

200

−1

First photon energy (cm ) − 36000 cm−

Figure 6.8: (a) Dissociation resonance accessed by two photons of total energy 71600–72400 cm−1 ,recorded by tuning the first photon to 35976 cm−1 and scanning the frequency of the second
photon. When scanning the dissociation resonance in (a), care was taken to step cleanly over any
one-photon transitions shown in (b). (b) HfF+ transitions accessed by a single photon of energy
35800–36200 cm−1 .

118
an approximate functional form due to complicating overlap details between the dissociating lasers
and the ion cloud. As a sanity check, the linear slopes of the two curves at small pulse fluence differ
by a ratio of 2.4, which is comparable to the ratio of the 266 nm beam areas in the two cases. The
saturation data indicates that as long as the ion cloud is smaller than the dissociation laser beams,
the dissociation transition can be saturated with the 266 nm pulse fluence being > 50 mJ/cm2 .
6
w0 = 5.0mm

5w = 3.3mm
0

Hf

+

4
3
2
1
0
0

50

100

150

266nm pulse fluence (mJ/cm2)

Figure 6.9: Saturation of the 1+1’ photodissociation transition with 266 nm laser pulse energy.
Two different beam waists were used for the 266 nm laser: (blue circles) w0 = 5.0 mm and (redtriangles) w0 = 3.3 mm. The saturation behavior is fit to a single exponential A(1 − exp(−F/FS )).
The smaller exponential amplitude for the smaller beam waist is due to a less complete spatial
overlap between the 266 nm laser and the ion cloud.

6.4.2

Efficiency of photodissociation

Saturating the dissociation transition does not necessarily guarantee that all the HfF+ ions ina single rovibronic state will be dissociated. Competition could arise between the photodissociation
process and radiative decay of the dissociating state down to a lower state of HfF+ , such thatthe photodissociation efficiency saturates with laser pulse energy to a value that is < 100%. To
understand the maximum achievable photodissociation efficiency for the repulsive curve accessed by
the 266 nm laser, we first ensured that both (1+1’) REMPD photons are saturating their respective
transitions, and that their beam waists are large enough so that spatial overlap with the ion cloud

119will not be an issue. We then reverted to creating HfF+ ions with a well-defined rotational state
distribution, i.e. by autoionizing neutral HfF such that 35% of the HfF+ is formed in the J = 0
rotational state of the ground vibronic level (shown in Chapter 3). The total HfF+ ion number
with and without the photodissociation lasers were then recorded, and we made sure that the MCP
detector was not saturated to reflect accurate ion numbers. The loss in HfF+ was 30% that of the
HfF+ ions in a single rovibronic state without dissociation, indicating that the photodissociation
efficiency is 30%. On the other hand, the HfF+ number loss was the same as the Hf+ ion number
detected, indicating that the detection efficiency of dissociated Hf+ ions is as high as 100%. The
overall efficiency of photodissociation as a state readout technique is therefore 30%, which is likely
to be limited by competition with other processes like spontaneous emission. The photodissociation
efficiency of 30%, nevertheless, is two orders of magnitude higher than that of LIF!

Chapter 7
Stimulated Raman transfer into 3 ∆1

The statistical sensitivity of an eEDM measurement is proportional to the square root of
the number of ions making the eEDM transition. An improvement to the statistical sensitivity
can come from a higher state detection efficiency, as offered by photodissociation over LIF, orfrom a larger initial population of ions in a particular |J, mJ , Ωi level of the 3 ∆1 (ν = 0) state.
In Chapter 3, we have shown that as many as 30% of the autoionized HfF+ can be populated
in a given |J, mJ i level of the ground 1 Σ+ (ν ′′ = 0) state using optical-optical double-resonanceautoionization. The autoionization technique can in principle be extended to form 3 ∆1 (ν = 0) ions.
One such example was the use of 308 nm + 355 nm as ionization lasers in the photodissociation
experiments. The Rydberg states accessed by the ionization lasers, however, underwent either
vibrational autoionization to form 3 ∆1 ions or electronic autoionization to form 1 Σ+ ions (i.e. theion core of the Rydberg state was in a different electronic state from the final ion formed). Electronic
autoionization is undesirable because it dilutes the ion population amongst multiple vibronic states.
It is plausible to embark on a search for a Rydberg state that only vibrationally autoionizes into the3 ∆ (ν = 0) state, yet this effort requires a clean understanding of the molecular orbital composition
1of both the Rydberg states and the neutral HfF intermediate states at ≈30000 cm−1 — a rather
daunting task for a molecule of which very little is known in general! Even in the best case scenario
where only vibrational autoionization is present, several rotational-hyperfine states of the 3 ∆1 will
still be populated besides the desired |J = 1, F = 3/2i state. Additional lasers will then be needed
to clean out population in the unwanted states.

121
An alternative to autoionizing directly into 3 ∆1 is the stimulated Raman population transfer
of ions from 1 Σ+ to the 3 ∆1 state. The excited state 3 Π0+ (ν ′ = 1) at 11115 cm−1 has been shownto have a strong electronic dipole moment and Franck-Condon overlap to both the 1 Σ+ and 3 ∆1states [16, 63]. The three levels form a Λ-type system (Fig. 7.1), of which the two lower levels |1i
and |3i couple to |2i via lasers of Rabi frequencies Ω1 and Ω3 respectively, but not directly to eachother. Ions can therefore be autoionized first into the 1 Σ+ state with a significant fraction in a given|J, mJ i level, and then transferred via a Raman process to the 3 ∆1 state. The stimulated Raman
transfer process can be adequately described using three-level physics — a coherent process withpotentially a huge efficiency for quantum sate manipulation! The physics and results of stimulated
Raman transfer are described in this chapter.

7.1

Basics of stimulated Raman transfer
In the rotating wave approximation, the Hamiltonian for the three-level system as illustrated

in Fig. 7.1 is described by the following matrix in the basis of states |1i , |2i and |3i:


Ω1
0 
 0


1

H =  Ω3 2∆ − iγ Ω3  ,

2


0
Ω1
2δ

(7.1)

where ∆ is the one-photon detuning from the excited state, δ is the two-photon detuning, andΩ1 , Ω3 are the Rabi frequencies of the lasers coupling |2i ← |1i and |2i → |2i, respectively. Eq. (7.1)
assumes that the ions that have decayed out of |2i (at a rate γ) completely leave the three-levelsystem. For the 3 Π0+ (ν ′ = 1, J ′ = 1) state, the probability of decaying back to either the 1 Σ+ (ν ′′ =0, J ′′ = 0) state or the 3 ∆1 (ν = 0, J = 1) state is less than 10% each. So, the Hamiltonian given by
Eq. (7.1) remains an adequate description. Had it been otherwise, the master equation approachshould be used instead of modeling the decay as an imaginary term in the Hamiltonian.
If the two-photon resonance condition is fulfilled (δ = 0), an eigenstate of the Hamiltonian is

122

(a)

3

P0+ (n’=1, J’=1)

(b)

|2ñ

|2ñ

D

D
|3ñ

W1

W3
|3ñ

|1ñ

W2g

d

|1ñ
1

D1 (n=0, J=1)

S (n’’=0, J’’=0)
+

|1ñ

3

|3ñ

d

Figure 7.1: (a) ‘Bare’ states used in the stimulated Raman transfer of population from |1i to |3i
via adiabatic elimination of |2i. The bare states are addressed by lasers of Rabi frequencies Ω1and Ω3 and of detunings ∆ and δ from the one-photon and two-photon transitions, respectively.
(b) Three-level system shown as “dressed” states; where the two-photon detuning δ is zero, thedressed states are symmetric and antisymmetric superpositions of the bare states |1i and |3i. The
point of closest separation in the avoided crossing is given by the two-photon Rabi frequency Ω2γ .
Individual ions are transferred from |1i to |3i as their velocities (and hence Doppler shifts) sweep
through zero with their secular motion in half a trap cycle.

123
the dark state |ψd i, which does not couple to the decaying excited state |2i:
|ψd i = p1
Ω21 + Ω23(Ω3 |1i − Ω1 |3i) .

(7.2)

Coupling to the dark state is one way of enabling population transfer from |1i to |3i without loss, by
first turning on the laser coupling Ω3 and then ramping on Ω1 while Ω3 is adiabatically turned off.
This technique has been very successful for the coherent population transfer of Feshbach molecules
to their ground state [60]. However, |ψd i is no longer an eigenstate once δ 6= 0, as is the case forthe eEDM experiment with trapped ions possessing two-photon Doppler widths of 3 MHz.
Instead of coupling to |ψd i, the population transfer with HfF+ ions can be carried out using
adiabatic elimination. Namely, the two transfer lasers are far-detuned from resonance to |2i, suchthat the off-resonant scattering rate from |2i is slow compared to the time it takes to perform thetransfer:γsc (∆) =≈γ
I/I0
2 1 + I/I0 + (2∆/γ)2
γ I  γ 2for large ∆ .
2 I0 2∆(7.3)

Applying the Schrödinger equiation to the Hamiltonian from Eq. (7.1) and with the state expressedas |ψi = c1 |1i + c2 |2i + c3 |3i, we obtain:
ic˙1 =
ic˙2 =
ic˙3 =

Ω1
c2 ,
2
γ
Ω3
Ω1
c1 + (∆ − i )c2 +
c3 .
2
2
2
Ω3
c2 + δc3 .
2(7.4a)(7.4b)(7.4c)

With adiabatic elimination, the population in |2i is unchanged over time, i.e. c˙2 = 0. The population
dynamics in the states |1i and |3i can then be described as i|ψ˙′ i = H2γ |ψ ′ i, where |ψ ′ i = c1 |1i +c3 |3i, andH2γ

where Ω2γ

≈
=



1

2

Ω21
2∆

Ω2γ

Ω1 Ω3
.
2∆

Ω2γ
Ω23

2∆ + 2δ




,

(7.5)

(7.6)

124
The two-photon effective Hamiltonian H2γ is the same as that for a two-level system with Rabi
frequency Ω2γ connecting the two states |1i and |3i. Fig. 7.1b shows the dressed state picture forthe three-level system with adiabatic elimination, where |1i and |3i are connected by an avoided
crossing and the frequency separation between the two crossings at the point of closest approachis given by Ω2γ . The two-photon detuning plotted on the horizontal axis needs to be swept (overtime Tsweep) slowly compared to (Ω2γ /2)2 to fulfill the adiabatic condition for efficient populationtransfer from |1i to |3i. More generally, the probability of adiabatically following the dressed
eigenstate is given by the Landau-Zener formula:(Ω2γ /2)2
PLZ (|1i → |3i) = 1 − exp −2π2δ/Tsweep



.

(7.7)

In the JILA eEDM experiment, the ions at 20 K experience one-photon Doppler shifts of±(2π)30 MHz. At some point during a half-trap cycle, each individual ion moves from positive tonegative velocities (or vice versa) and sweeps through the two-photon detuning of ±(2π)3 MHz indoing so. (The two-photon detuning of the Λ-system is about one-tenth that of the one-photon
Doppler shift because the difference in frequency between the two transitions is one-tenth of any
one of the transition frequencies.) Therefore, the stimulated Raman transfer is simply performedby leaving both co-propagating transfer lasers on simultaneously for a half-trap cycle (Tsweep =π/ωtrap ). As long as Ω2γ is large enough to fulfill the adiabatic condition, the Raman transfer will
be efficient (>50%). However, where Ω2γ is small, the transfer lasers will have to be left on for
multiple half-trap cycles. In subsequent half-trap cycles, the population transfer is no longer fully
coherent, i.e. ions can also be transferred back from |3i to |1i, so that over time the population
equilibrates to 50% in either |1i or |3i. All this assumes that the population in |2i is small due tothe adiabaticity of the transfer process.

125

7.2

Estimation of Raman transfer parameters

7.2.1

Strategy

Eq. (7.7) describes the Raman transfer efficiency that can be accomplished for a given setof Rabi frequencies, one-photon detuning, two-photon detuning and sweep time. Several of these
crucial parameters were not yet experimentally established before we started building the Raman
transfer experiment, namely: the lifetime of the 3 Π0+ excited state, which sets an upper limit on
Tsweep, and the Rabi frequencies for both transitions {Ω1 , Ω3 }. The Rabi frequency Ωi is related
to laser intensity Ii by the following:
1
1
Ii = ǫ0 cEi 2 = ǫ0 c
2
2



~Ωi
h2 |d| ii



2

,

(7.8)

where h2 |d| ii is the rovibronic transition dipole matrix element between |2i and |ii = |1i , |3i. In
the limit of infinite laser intensity or negligible Doppler shift, the Raman transfer efficiency can beas high as 100%. However, as mentioned at the end of Section 7.1, the two-photon Doppler shift is±(2π)3 MHz. Additionally, since the laser power is finite and the ions are spread across a 3 mm 2σradius cloud, the Raman transfer laser intensity is limited. It is therefore important to first estimate
the 3 Π0+ lifetime and the Rabi frequencies that can be achieved with reasonable laser intensities.
The main unknowns related to the lifetime and Rabi frequencies are the rovibronic transition
dipole matrix elements h2 |d| ii. Specifically, the electronic components of these transition dipole
matrix elements3Π
1 +0+ |d| Σand3Π
30+ |d| ∆1

require more work to be determined, since thevibrational and rotational dipole matrix elements can be easily calculated from the vibrational
wavefunction overlap and Clebsch-Gordan coefficients.
Unfortunately, of the HfF+ data available to us, none are directly related to the transition
dipole matrix elements we need to calculate:(1) Transitions to the 3 Π0+ state have been identified spectroscopically by performing velocity
modulation spectroscopy in a discharge tube at ≈850 K, but the density of populations is
not normalized, making an absolute measurement of the transition dipole matrix elements

126
impossible. On the other hand, it is plausible to extract the relative ratio of the relevanttransition dipole matrix elements from the spectroscopic intensities.
(2) Petrov et. al. had directly calculated3Π
1 +0+ |d| Σand3Π
30+ |d| ∆1from ab-initio

theory [63], but given the large uncertainty in the other ab-initio results (e.g. transition
frequencies), we would prefer to extract the absolute transition dipole matrix elementsfrom experiment. Nevertheless, it is interesting to note that the ratio ofto3Π
30+ |d| ∆13Π
1 +0+ |d| Σ

reported in [63] falls within 30% of that extrapolated from the velocity

modulation spectroscopy data, so we also use the theoretical ratio of dipole matrix elements
to guide our estimations.
(3) LIF experiments of HfF+ ions have yielded both the lifetime of the excited state andsaturation fluence of the LIF transition, but the LIF transition is that between 1 Σ+ and 1 Π1 .
The lifetime and saturation fluence measurements provide independent ways to estimate
1 Π |d| 1 Σ+
1, but neither of the two methods yield a transition dipole matrix element

connecting to the 3 Π0+ state.
Given the above data and constraints, the strategy to estimate
is as follows: we first calculate

1 Π |d| 1 Σ+
1

3Π
1 +
0+ |d| Σand 3 Π0+ |d| 3 ∆1in two ways using the two LIF measurements of life-

time and of saturation fluence; the extent to which the two extracted dipole matrix elements agreewith each other gives us some measure of faith in the accuracy of our LIF measurements. We thenrelate1 Π |d| 1 Σ+
1

to

3Π
0+ |d| ψel,iusing the ratios of dipole matrix elements available fromboth the velocity modulation spectroscopy data and Petrov et. al.ś calculations. Finally, we account for vibrational and rotational wavefunction overlaps to obtain the total rovibronic transition
dipole matrix elements h2 |d| ii, with which we estimate the 3 Π0+ state lifetime and Raman transfer
Rabi frequencies.

127
7.2.2

Estimation of

1 Π |d| 1 Σ+
1from an LIF measurement of the 1 Π1 lifetime

We first present one of two ways to estimate the transition dipole matrix element

1 Π |d| 1 Σ+
1i.e. from an LIF measurement of the 1 Π1 decay lifetime. The 1 Π1 is most likely to decay to either
1 Σ+ or 3 ∆ , as indicated by the electronic transition dipole matrix elements given in Table 7.12[64, 63]. The observed decay rate is then the sum of decay rates to the individual lower electronic
and vibrational states:1τ (1 Π1 , ν ′ = 0)
where

≈

X
ν

1
1
+ 1
,
1 Π , ν ′ = 0 → 1 Σ+ , ν ′′ )′ = 0 → 3 ∆ , ν ′′ )
τ
(
τ
(
Π
,
ν
1
1
2
′′

2e2
1
=
ω3
τ (1 Π1 , ν ′ = 0 → ψel,i , ν ′′ )3ǫ0 hc3

ν ′ = 0|ν ′′1

Π1 |r| ψel,i

2

.

(7.9)

(7.10)In Eq. (7.10), ω refers to the radial frequency difference between the 1 Π1 (ν ′ = 0) and ψel,i (ν ′′ )levels (see Table 7.2 for a table of electronic energies and [4] for a list of vibrational energies). Due
to diminishing Franck-Condon factors, only the first four vibrational levels of the lower electronic
state are summed over in Eq. (7.9).
To measure the lifetime of the 1 Π1 (ν ′ = 0) state, the decay of fluorescence photons wasmeasured on a photomultiplier tube as a function of delay time after firing the LIF laser. Fig. 7.2
shows the measured lifetime of the 1 Π1 (ν ′ = 0) state to be 1.15(4) µs. The measured lifetime
is close to the predicted lifetime of 0.86 µs calculated from the transition dipole matrix elements
1 Π |d| ψ1el,iin Table 7.1. If the relative values of the transition dipole matrix elements are to betrusted, the dipole matrix elements only need to be scaled by an overall factor of 0.87 to match themeasured lifetime, which gives

1 Π |d| 1 Σ+
1

= 0.48 e a0 .

Table 7.1: Calculated transition dipole matrix elements (in ea0 ) between states of HfF+ given by
the corresponding row header and column header [64]. If denoted by an asterisk, that value isobtained from Reference [63].
1 Σ+
1Π
1
3Π
0+

0.55
0.15

3∆

1

0.03
0.27

3∆

2

0.18
0∗

3∆

0∗

0∗

3

1∆

2

0.021∗
0∗3Π
0+0.002∗

3Π
1

3Π
2

0.135∗-0.006∗,

LIF photon counts

128

0.15

τ = 1.15(4) µs

0.1
0.05
0
−0.05

0

2
4
Time (µs)

6Figure 7.2: Lifetime of the 1 Π1 (ν ′ = 0) state measured using LIF.

129
Measured and calculated electronic energies (in cm−1 ) of ground and excited states inTable 7.2:
HfF+ . By default, the reported values are measured by Cossel et. al. [16]. If denoted by a dagger
sign, the reported value was measured by Barker et. al. [4]. If denoted by an asterisk, that value
was calculated by Petrov et. al. [63].
1 Σ+

0

7.2.3

3∆

1

977

Estimation of

3∆

3∆

2
2166†

3
3951†

1 Π |d| 1 Σ+
1

The dipole matrix element

1∆

211519∗

3Π
0+

3Π
1

1Π
1

3Φ

10402

10895

13002

13933

2

from LIF measurements of the saturation fluence

1 Π |d| 1 Σ+
1

can also be estimated from measurements of the

LIF saturation fluence, F = hν/σ, where ν is the transition frequency and σ is related to theRintegrated cross section σ0 = σ(ω)dω:
σ0 =πω
3g1 ǫ0 ~cν ′ = 0|ν ′′ = 0

1

Π1 |d| 1 Σ+

2

SJ ′ ,J ′′ 2 ,(7.11)

where g1 is the degeneracy of the lower state and SJ ′ ,J ′′ 2 is the rotational line intensity given by
the Hönl-London factor. (Note that among the different rotational lines that can be probed, theR(0) line gives g1 /SJ ′ ,J ′′ 2 = 1 whereas the Q(n) lines give g1 /SJ ′ ,J ′′ 2 = 2, which is consistent with
our observation that the saturation fluence for the R(0) line is half that of the Q(1) or Q(2) line.)
To obtain σ0 from σ, we assume the ions are Doppler-broadened with a Doppler width ofσνdopp= (2π) 30 MHz. Since the Gaussian profile shares the same area as a top-hat profile of the√ σTH, we can make the approximation
same amplitude and of a top-hat full width νdopp= 2 2νdoppTH
σ0 = σνdopp.

(7.12)

Combining Eqs. (7.11) and (7.12), the electronic transition dipole matrix element is related
to the observed saturation fluence via
1

Π1 |d| 1 Σ+ =1′hν = 0|ν ′′ = 0irTH
3ǫ0 c~2 νdopp

g1.
πFSJ ′ ,J ′′ 2

(7.13)The observed saturation fluence from LIF studies was F = 0.52 µJ/cm2 for the R(0) line (g1 = 1),
from which we determined

1 Π |d| 1 Σ+
1

= 0.35 e a0 . This electronic transition dipole moment

130
is 40% smaller than that estimated in Section 7.2.2, but is nevertheless on the same order ofmagnitude.

7.2.4

Estimation of 3 Π0+ lifetime and Rabi frequencies for Raman transfer

To obtain the transition dipole matrix elements

3Π
1 + 3
0+ |d| Σ , ∆1

from1 Π |d| 1 Σ+
1

, we

can use the following methods:(1) Measure the relative intensities of the 1 Π1 ← 1 Σ+ , 3 Π0+ ← 1 Σ+ and 3 Π0+ ← 3 ∆1 vibronic bands as observed in velocity modulation spectroscopy [16], and then account for
the Franck-Condon overlaps to get only the relative magnitudes of electronic dipole matrix
elements. The relative electronic dipole matrix elements are then scaled by an overall factor
to match the estimated dipole matrix elements of

1 Π |d| 1 Σ+
1from either Sections 7.2.2

or 7.2.3. Such scaling assumes a certain temperature distribution of electronic levels in thevelocity modulation discharge tube setup, for which there is unfortunately no self-consistent
check.
(2) Use the dipole matrix elements provided by Petrov and Titov in Table 7.1, but scale themby an overall factor to match

1 Π |d| 1 Σ+
1from either Sections 7.2.2 or 7.2.3.

From the electronic transition dipole matrix elements and Franck-Condon overlaps, the lifetime of the Raman transfer excited state 3 Π0+ can be estimated using the same formulas asEqs. (7.9) and (7.10) but substituting for the lower electronic levels ψel,i = 1 Σ+ , 3 ∆1 . Further,
the transfer laser Rabi frequencies Ωi can be calculated from a given laser intensity Ii by inverting
Eq. (7.8). More explicitly,Ωi =3

Π0+ |d| ψel,i′′′ν |ν = 0

F ′ J ′ m′ Ω′
SF ′′ J ′′ mF′′ Ω′′
F

1
~

r

2I
ǫ0 c

,

(7.14)

131
whereF ′ J ′ m′ Ω′

SF ′′ J ′′ mF′′ Ω′′F=p(2F ′ + 1)(2F ′′ + 1)(2J ′ + 1)(2J ′′ + 1)





′
′′
′
′′
 J ′′ F ′′ I 

1
J 
1
F  J F.
(7.15)
′′′′′′ F ′ J′ 1  −m′ m′ − m′′ m′′−Ω Ω − Ω ΩFFFFThe choice of rotational and hyperfine levels to be used for the population transfer warrants
some careful consideration. In 180 Hf19 F+ , the nuclear hyperfine number is I = 1/2, so each mJlevel is further split into two mF levels. To measure the eEDM transition frequency, the ions need
to be populated in the state |F = 3/2, J = 1, mF = 3/2, Ω = 1i. Given our ability to populate as
many as 30% of the HfF+ in |J ′′ = 1, m′′J = −1, Ω′′ = 0i of the 1 Σ+ ground state and assuming
equal population in each m′′F sub-level of the |m′′J = −1i state, we can populate 15% of the HfF+
in |F ′′ = 3/2, J ′′ = 1, m′′F = 3/2, Ω = 0i. The path that yields the strongest two-photon rotational
|2i

|3i

amplitude S|1i S|2i is then provided by the transitions 1 Σ+ (|F ′′ = 3/2, J ′′ = 1, m′′F = 3/2, Ω′′ = 0i)→ 3 Π0+ (|F ′ = 1/2, J ′ = 0, m′F = 1/2, Ω′ = 0i) → 3 ∆1 (|F = 3/2, J = 1, mF = 3/2, Ω = 1i), which
can be made by a σ − -polarized photon followed by a σ + -polarized photon. This transfer scheme
works well only if the quantization axis is fixed, as is often the case in atomic physics experiments
to be either the direction of laser propagation or the direction of an external magnetic or electricfield.
In the eEDM experiment, the externally applied electric field used to polarize the molecule
has to be constantly rotating to keep the ions trapped. The quantization axis, which is set by theelectric field, is therefore constantly rotating as well. This means that even though 15% of the HfF+
can be autoionized into a single m′′F level when the electric field is aligned with the direction of laser
propagation, the different m′′F levels will be remixed as the quantization axis rotates. Since theminimum time required for the Raman transfer, which is half a trap cycle, translates to multiple
rotation cycles (ωrot ≫ ωtrap ), the fraction of ions occupying any one of the six m′′F levels in J ′′ = 1
will be time-averaged to one-sixth of the total population in the J ′′ = 1 level. From Chapter 3,
we showed that the autoionization process gave 60% yield in the J ′′ = 1 level, which means that132
the fraction of ions in a single |J ′′ = 1, m′′F i state is only 10%. On the other hand, the sameautoionization line, accessed through an intermediate state of the opposite parity, can yield 35% of
the HfF+ in the J ′′ = 0 state, where the J ′′ = 0 only has two m′′F levels. As many as 17.5% of the
HfF+ can therefore be populated in one of the two m′′F levels in (F ′′ = 1/2, J ′′ = 0). Due to parity
selection rules, the 3 Π0+ (J ′ = 0) ← 1 Σ+ (J ′′ = 0) transition is forbidden. The best case scenario
is then to first make a R(0) transition on the upward transfer leg (Ω1 ) and then a Q(1) transitionon the downward transfer leg (Ω3 ). For a single Raman transfer leg, the rotational amplitude |S|is then calculated by first summing over the rotational line intensities to the different unresolved
final states and averaging over the number of initial states, and then taking the square root of thatquantity.
Table 7.3 summarizes the 3 Π0+ (ν ′ = 1) lifetime and Rabi frequencies Ω1 , Ω3 for reasonabletransfer laser intensities of 1 W/cm2 . The electronic transition dipole matrix elements
displayed in the table are extrapolated from the average of the two values for3Π
0+ |d| ψel,i

1 Π |d| 1 Σ+1

as cal-culated in Sections 7.2.2 and 7.2.3.
Table 7.3: Electronic transition dipole matrix elements 3 Π0+ |d| ψel,i , lifetime of 3 Π0+ (ν ′ = 1),
and Rabi frequencies Ω1 , Ω3 that can be achieved with a 1 W/cm2 laser. With the help of (a) relative
intensities measured in velocity modulation spectroscopy or (b) relative dipole matrix elements
presented in Table 7.1, the transition dipole matrix elements 3 Π0+ |d| ψel,i are estimated fromthe average value for 1 Π1 |d| 1 Σ0 as calculated in Sections 7.2.2 and 7.2.3. The Rabi frequenciesΩ1 and Ω3 are calculated for the transition 3 Π0+ (ν ′ = 1, J ′ = 1) ← 1 Σ+ (ν ′′ = 0, J ′′ = 0) and3 Π (ν ′ = 1, J ′ = 1) → 3 ∆ (ν = 0, J = 1) respectively.
0+13Π
1 + (ea )0+ |d| Σ
03Π
3 ∆ (ea )
|d|
0
0+
1
τ (3 Π0+ , ν ′ = 1)(µs)Ω1 /(2π) (MHz)Ω2 /(2π) (MHz)

(a)
0.116
0.164
15
2.5
2.1

(b)
0.114
0.204
16
2.5
2.7

133

7.3

Experiment setup
To perform stimulated Raman transfer to the 3 ∆1 state via the 3 Π0+ (ν ′ = 1) excited state,

the transfer lasers for the upward and downward leg need to be tuned to 899.7 nm and 986.4 nm,
respectively. The 899.7 nm home-built laser is the output of a 1.5 W tapered amplifier injected bylight from an external cavity diode laser (ECDL), while the 986.4 nm laser is a Toptica DL Pro
laser, which is also an ECDL seeding a 2 W tapered amplifier. Both the home-built and Toptica
laser have extended mode-hop-free tuning ranges offered by feeding forward the ECDL grating
position (via the piezoelectric stack’s control voltage) onto the diode current [22].
The two transfer lasers need to have their relative frequencies stabilized to much better than
the inverse of the time the ions take to traverse the adiabatic crossing (illustrated in Fig. 7.1b),which is typically1
2 ωtrap δ=≈ 2 × 105 s−1 .
Ttransf er
πΩ2γ(7.16)The High Finesse WS7 wavemeter that is used to measure the absolute wavelengths of the twotransfer lasers only has an accuracy on the order of 10 MHz. To stabilize the lasers to a maximum
relative linewidth of ≪ 30 kHz, the 899.7 nm and 986.4 nm lasers are locked to an optical cavityof finesse 1500 and 3000 for the two wavelengths respectively. The details of the cavity lock setup
are beyond the scope of this thesis and will be discussed in Kevin Cossel’s thesis. Briefly, tocenter the desired laser frequencies on a cavity resonance (free spectral range = 1.3 GHz), the laser
frequencies are offset by AOMs before sending them through the cavity: the 899.7 nm laser is offset
by a double-passed acousto-optical modulator (AOM) at 2 × 260 MHz, and the 986.4 nm laser isfirst offset by a 800 MHz AOM and then a double-passed AOM at 2 × 200 MHz. Each laser is thenlocked using a Pound-Drever-Hall lock [21]. The linewidth of a single locked laser is measured tobe 10 kHz, which is also an upper bound on the relative frequency jitter between the two lasers.
In a search for the two-photon resonance (δ = 0), we scanned the transfer laser frequencies bytuning the frequencies of the double-passed AOMs while keeping the lasers locked to the cavity. The
long-term stability of the cavity, enabled by placing the cavity in a sealed and evacuated vacuum

134chamber that is temperature stabilized to 0.01◦ C, was good enough such that the two-photon
resonance line (shown in Section 7.5) drifted by less than 100 kHz over two weeks.
The two transfer lasers are switched on and off using AOMs as shutters before being fibercoupled to the ion trap setup. Light from both lasers is then directed onto the ions through the top
electrode/light pipe of the ion trap. The axial direction of laser propagation was chosen so as to beinsensitive to the circular micromotion from the application of a rotating field in the radial plane,
which can cause the ions to exhibit Doppler widths as large as σD = (2π)480 MHz. To achievereasonably high Rabi frequencies (> (2π)4 MHz), the 150 mW transfer lasers are telescoped down
to a beam waist of w = 1 mm. The spatial overlap between the smaller transfer laser beam waist
and the ion cloud was improved by ramping the trap frequencies in the radial directions up to(2π)11 kHz, which squeezed the ions to a radial width of σi = 0.8 mm. The axial trap frequency
was simultaneously ramped down to ωtrap ≡ ωz = (2π)0.85 kHz, which not only cooled the ions togive a smaller axial Doppler width (also the two-photon detuning δ), but also increased the sweep
time for the transfer Tsweep , making the Raman transfer occur more efficiently as described by
Eq. (7.7).
To detect the ion number in either the 1 Σ+ state or the 3 ∆1 state, we employed the UVdoubled output of a pulsed dye laser to provide the first photon and 266 nm (provided by thesame Nd:YAG pumping the dye laser) as the second photon to access the dissociating state. The
first photon of the dissociation laser was tuned to resonance between the relevant lower state andthe upper state [35.97]Ω′ = 0, where the spectroscopic constants for the upper state have beencharacterized in the previous chapter. At a pulse energy of 100 µJ and a linewidth of 0.12 cm−1 ,the first dissociation photon is sufficient to resolve individual rotational states but not providing
any finer resolution (e.g. it cannot address individual hyperfine or Ω-doublet levels). This levelof resolution turns out to be a convenient feature in performing spectroscopy of the 3 ∆1 level(Section 7.5), where the dissociation laser frequency does not have to be changed in order to accessdifferent hyperfine or parity levels.

135

7.4

Rabi frequency calibration
Before performing the stimulated Raman transfer, we are interested in a direct measurementof the Rabi frequency for a given applied laser intensity, to provide both a check against the Rabi
frequency estimates presented in Section 7.2 and to obtain a better sense of our success with Raman
transfer. For such a Rabi frequency calibration, only one of the two transfer lasers is used and istuned to resonance between the relevant lower state |ii and the upper state |2i.
Using a laser of some measured intensity, the efficiency of transferring ions from |ii to |2i ina half-trap cycle Tsweep is given by the Landau-Zener probability:(Ωi /2)2.
PLZ (|ii → |2i) = 1 − exp −2π2∆/Tsweep
Eq. (7.17) is now derived for a two-level Hamiltonian, written in the {|ii , |2i} basis as
1  0 Ωi 
Hi = 
,2Ωi 2∆(7.17)(7.18)

where Ωi is the one-photon Rabi frequency (to be determined) and ∆ is the one-photon Doppler
shift. The analytical result with ∆ calculated from the standard deviation of a Gaussian-distributed
velocity spread is very similar to the numerical result obtained by thermally averaging over thewhole velocity distribution.
Once populated in |2i, the ions spontaneously decay quickly compared to a half-trap cycle, sothat in subsequent half-trap cycles, the ions are not transferred from |2i back to |ii. The probabilityof decay in a single half-trap cycle can then be cleanly determined by leaving on the transfer laser
for multiple half-trap cycles and measuring the exponential time constant τi for the ions to be
depleted from state |ii:
N1 Σ+ (t)= e−t/τ1 = [1 − PLZ (|ii → |2i)]t/Tsweep
N1 Σ+ (t = 0)
from which we can determine the Rabi frequency:(Ωi /2)2tt
2π= exp −exp −τiTsweep2∆/Tsweepr4∆⇒ Ωi =
πτi(7.19)(7.20)

136
The Rabi frequency calibration method assumes that the ion cloud is well-overlapped with thelaser, so that there are no ions on the laser beam periphery that can take a longer time to movethrough the laser radially and be depleted less efficiently. To avoid the spatial overlap issue, thelaser beam is expanded to three times the ion cloud width. The fact that the Rabi frequency isdecreased with a larger beam waist is immaterial for this experiment because we are only interested
in calibrating the Rabi frequency as a function of laser intensity.
As a sanity check, we first performed the Rabi frequency calibration on the 1 Π1 (ν ′ = 0, J ′ =1) ← 1 Σ+ (ν = 0, J = 1) LIF transition, for which the dipole matrix element has already been
estimated from two prior LIF measurements. Fig. 7.3a shows the number of 1 Σ+ ions depleted as afunction of the trap time for a diode laser intensity of 0.49 mW/cm2 . The depletion in ion number
is read out as the difference in 1 Σ+ ions photodissociated with and without the LIF laser. The
depletion follows an exponential decay, from which the Rabi frequency is extracted using Eq. (7.20).
p
Fig. 7.3b is a plot of the Rabi frequency versus the laser electric field E = 2I/(ǫ0 c), from which

the slope yields the combined rovibronic dipole matrix element to be 0.098(13) e a0 . Accounting
for the vibrational and rotational dipole matrix elements, the measured electronic dipole matrix
element is

1 Π |d| 1 Σ+1

= 0.23(3) e a0 , which is 2.1 and 1.5 times smaller than that estimatedfrom LIF lifetime and saturation fluence measurements respectively.
Although the sanity-check experiment did not agree with previous estimates particularly well,
we proceeded with the same method of Rabi frequency calibration for the 3 Π0+ (ν ′ = 1, J ′ = 1) ←1 Σ+ (ν= 0, J = 0) upward leg of the Raman transition. Fig. 7.3c shows the summary plot of

Rabi frequency versus 899.7 nm laser electric field, and the slope gave a combined rovibronic dipole
matrix element to be h2 |d| 1i = 0.065(9) e a0 . The combined rovibronic matrix element is the most
relevant for the stimulated Raman transfer experiment; expressed in a more practical manner, themeasured rovibronic matrix element would give Ωi = (2π)2.3(3) kHz for an intensity of 1 W/cm2 .
On the other hand, one might again be curious about how the measured electronic dipole matrix
element compares against the estimated values in Table 7.3. In this case, the electronic dipole
matrix element is measured to be 0.08(1) e a0 , which is comparable to the estimated values.

137

3
2
1

τ = 4.0(9) ms0+

Hf counts per shot(∝ depleted HfF+ in 1Σ+)

(a)

0

20

40

60

80

100

0.2
0.15

1

Π ← 1Σ+
1

0.1
0.05
0

0

0.5

1

Electric Field (V/cm)

(c)

0.2

Ω/(2π) (MHz)(b)Ω/(2π) (MHz)

LIF laser duration (ms)

0.15

3

Π

0+

← 1Σ+

0.1
0.05
0

0

0.5

1

1.5

Electric Field (V/cm)

Figure 7.3: (a) Number of HfF+ ions transferred out of the 1 Σ+ state (detected as the difference indissociated Hf+ counts with and without the LIF laser) as a function of LIF laser duration, where
the LIF laser is tuned to resonance with the 1 Π1 (ν ′ = 0, J ′ = 1) ← 1 Σ+ (ν ′′ = 0, J ′′ = 1) transition.
For this data, the Doppler width (one-photon detuning ∆) was anomalously large at 120 MHz.
Nevertheless, the decay time constant of 4.0(9) ms, which is measured for a particular LIF laser
intensity of 0.49 mW/cm2 , can be converted to a LIF laser Rabi frequency of (2π)0.078(9) MHz
and plotted as a single point in (b). (b) Plot of Rabi frequency versus laser electric field for the1 Π (ν ′ = 0, J ′ = 1) ← 1 Σ+ (ν ′′ = 0, J ′′ = 1) LIF transition. The slope gives the rovibronic transition
1
dipole moment to be 0.098(13) e a0 . (c) Plot of Rabi frequency versus laser electric field for the3 Π (ν ′ = 1, J ′ = 1) ← 1 Σ+ (ν ′′ = 0, J ′′ = 0) transition. The slope gives the rovibronic transition0+
dipole moment to be 0.065(9) e a0 .

138
In principle, we should also be able to extend the Rabi frequency calibration technique toΩ3 , where the lower state is the 3 ∆1 state. Prior to attempting the stimulated Raman transfer, wepopulated the 3 ∆1 by using a 355 nm photon as the second photon in autoionization. However, theexponential depletion process was measured to be very noisy with the 3 ∆1 state regardless of thelaser intensity, and we were unable to trust the Rabi frequency obtained; one possible reason was a
low number of HfF+ ions that autoionized into the 3 ∆1 level. On the other hand, after performing
the stimulated Raman transfer, we were able to cleanly deplete 3 ∆1 ions by sending a on-resonant
986.4 nm laser onto the ions through one of the trap radial directions with the rotating bias field
turned on at ωrot = (2π)253 kHz. This side-depletion laser (also expanded to ensure full overlap
with the ions) was only strobed on with a duty cycle of 20% when the rotating field is pointing
along the direction of propagation of the laser. In this case, the one-photon detuning was dominatedby the Doppler shift of the circular micromotion to be (2π)480 MHz and Tsweep = 2π/ωrot . By
measuring the exponential decay time constant to be 0.89(2) ms for a 70 mW/cm2 beam, we
determined the rovibronic dipole matrix element to be h2 |d| 1i = 0.04(1) e a0 , or that we should
expect a Rabi frequency of 2(π)1.4(4) MHz per mW/cm2 of laser. The measured rovibronic dipole
matrix element in turn implied an electronic dipole matrix element of 0.11(3) e a0 , which is about
1.7 times weaker than that in Table 7.3.

7.5

Results of stimulated Raman transfer

7.5.1

Spectroscopy of hyperfine levels in 3 ∆1 (ν = 0, J = 1)

Having obtained a rough calibration of the Rabi frequencies, we attempted to perform thestimulated Raman transfer, with the HfF+ ions created only in the 1 Σ+ (ν ′′ = 0) state, of which
35% were formed in the J ′′ = 0 level. To search for the two-photon resonance (δ = 0), the 899.7 nm
laser frequency was fixed to be red-detuned from the |2i ← |1i transition by ∆ = (2π)80 MHz,
while the 986.4 nm laser was scanned in frequency. The photodissociation laser was tuned to readout HfF+ ions in the 3 ∆1 (J = 1) state and no rotating bias field was applied. Fig. 7.5a shows the139

Depletion Efficiency

0.8
0.6
0.4

τ = 0.89(2) ms

0.2
0
0

2
3

4

6

8

10

3

( Π0+ ← ∆1) laser duration (ms)Figure 7.4: Depletion efficiency of the 3 ∆1 HfF+ ions as a function of the 986.4 nm side-depletion
laser duration, where the 986.4 nm laser of intensity 70 mW/cm2 is tuned to resonance with the3 Π (ν ′ = 1, J ′ = 1) ← 3 ∆ (ν = 0, J = 1) transition. The decay time constant of 0.89(2) ms
0+
1
implies a rovibronic dipole matrix element of 0.04(1) e a0 .

140number of 3 ∆1 ions dissociated into Hf+ ions as a function of the 986.4 nm laser frequency. The
two signal peaks are the two hyperfine levels of the 3 ∆1 (J = 1) state: F = 1/2 and 3/2 (Fig. 7.5b).
(The signal for the frequency region in between the two peaks has been measured to be zero inother data sets not shown.) The hyperfine splitting is measured to be EHF =46.5(2) MHz, whichlies in the range of the theoretical estimate of 33.9–58.1 MHz [62].

|2ñ

(b)
F = 3/2

10

F = 1/2

W1

5+

Hf counts

(a)

0
-60

-40

-20

0

Two-photon detuning δ (MHz)

20

W3
|3ñ
d

F=1/2
F=3/2

J=1

|1ñ

Figure 7.5: (a) Hyperfine spectroscopy of the 3 ∆1 (ν = 0, J = 1) state. (b) Bare states used in thestimulated Raman transfer, with the 3 ∆1 (J = 1) hyperfine levels explicitly denoted.

To figure out the Raman transfer efficiency, we tuned the photodissociation laser to detect the
number of HfF+ ions depleted from the 1 Σ+ (J ′′ = 0) state when the Raman transfer is performed.
Fig. 7.6a shows the dissociated Hf+ signal as a function of transfer time, measured without any
transfer lasers (black crosses), and with the 899.7 nm laser turned on but with (blue dots) andwithout (red open circles) the 986.4 nm laser. Both lasers are tuned to the two-photon resonancefor transfer to the 3 ∆1 (F = 3/2) level. In the absence of any transfer lasers, the HfF+ ion number
remains roughly constant at N0 . With the 899.7 nm laser only, the number of HfF+ ions (N1 )decreases slowly over time due to off-resonant optical pumping of the HfF+ ions out of the 1 Σ+ (J =1) state into other rovibronic states. With both transfer lasers, the HfF+ ions (N2 ) are depleted
more quickly, and the efficiency of depleting 1 Σ+ ions, η = (N1 − N2 )/N1 , saturates to 53(3)% inseveral half-trap cycles (Fig. 7.6b). Since some of the ions depleted by off-resonant optical pumping(N0 − N1 ) are ions that would have also undergone stimulated Raman transfer with both lasers,
the Raman transfer efficiency is bounded to be between 53(3)% and (N0 − N2 )/N0 = 67(2)% after

141
multiple half-trap cycles.
The fact that the multiple half-trap cycles are needed to saturate the Raman transfer efficiency means that the population of ions in the 3 ∆1 level comes from equilibrating with the ion
population in the initial 1 Σ+ level. The expected efficiency of ions transferred can then be givenby the ratio of degenerate states in the final 3 ∆1 level to the total number of states involved. Moreexplicitly, there are two |m′′F i states in the initial 1 Σ+ level, and eight |F = 3/2, mF i states and four
|F = 1/2, mF i states in the final 3 ∆1 level.The ratio of degenerate states is then R = 8/(8+2) =0.8 or 4/(4+2) = 0.67 for the F = 3/2 and 1/2 final states, respectively. However, parity selection
rules dictate that in the absence of any electric fields mixing the 3 ∆1 states of opposite parity, there
are only four F = 3/2 and two F = 1/2 states available for the Raman transfer, which changes theratio of final states to total states to R =4/(4+2) = 0.67 or 2/(2+2) = 0.5 respectively (Fig. 7.7a).
In the absence of the rotating bias electric field, it is not clear the extent to which the trapping
fields are able to mix the states of opposite parity (Fig. 7.7b), so the transfer efficiency, barring
any technical issues, is expected to be in the ranges of 0.67–0.8 and 0.5–0.67 for the F = 3/2 and1/2 levels. In any case, R is consistently higher for the F = 3/2 hyperfine level, which accounts
for the slight increase in ions transferred to the F = 3/2 level over the F = 1/2 level as observedin Fig. 7.5a.

7.5.2

Stark spectroscopy with a rotating bias field

In the absence of an external bias electric field, the 3 ∆1 states of opposite parity, separated√√
by ωef , are given by: |−i = (|Ω = +1i − |Ω = −1i)/ 2, |+i = (|Ω = +1i + |Ω = −1i)/ 2, where‘+’/‘−’ denote the total parity of the state. With the rotating bias electric field strong enough tomix the states of opposite parity, Ω becomes a good quantum number and the mF levels undergoa linear Stark splitting in the molecular frame:
ES = −mF Ω γF dmf Erot + EF

(assume dmf Erot ≫ ωef ) ,(7.21)

142

+

+

1 +

Hf counts (∝ HfF in Σ )(a)Fraction of
1 ++( Σ )HfF depleted

(b)

50

No transfer lasers (N0)899.7nm laser only (N1)40

Both transfer lasers (N2)

30
20
10
0
1
(N − N )/N = 0.67(2)
0

0.8

2

0

0.6
0.4
(N − N )/N = 0.53(3)
1

2

1

0.2
0

0

2
4
6
8
Transfer duration (ms)10

Figure 7.6: (a) HfF+ ions (detected as dissociated Hf+ ) as a function of transfer laser duration
for the cases of (blue dots) both transfer lasers present, (red open circles) 899.7 nm laser present
only, and (black crosses) no transfer lasers. The 899.7 nm laser causes a slow off-resonant opticalpumping of HfF+ out of the 1 Σ+ state over time. The presence of both transfer lasers depletes
the 1 Σ+ ions more quickly. (b) Fraction of HfF+ ions depleted from the 1 Σ+ state, determinedfrom the data shown in (a) as either (red) (N1 − N2 )/N1 or (black) (N0 − N2 )/N0 . The depletion
fraction, which is expected to be the same as the transfer fraction, saturates after a few millisecondsof transfer time.

143|2ñ J’’ = 1 (-)|2ñ J’’ = 1 (-)

(a)

(b)

F

|3ñ
+
J’’ = 0 (+)
F’’ = 1/2

|1ñ

|3ñ

1/2

+ 3/2
mF: -3/2 -1/2 1/2 3/2

F
1/2

J’’ = 0 (+)
F’’ = 1/2

|1ñ

3/2
mF: -3/2 -1/2 1/2 3/2

Figure 7.7: Bare states involved in the stimulated Raman transfer with their parities denoted as‘+’ or ‘−’. (a) In the absence of an external electricfield, the 3 ∆1 energy levels are states of well√defined parity: |±i = (|Ω = +1i ± |Ω = −1i)/ 2. Parity selection rules dictate that only − ↔ +transitions are allowed, so only the |+i states of the 3 ∆1 manifold can be populated. (b) In a weakelectric field that is still sufficient to mix states of opposite parity without giving rise to a large
Stark shift, all 12 states of the 3 ∆1 may be populated in Raman transfer.

144
where EF is the offset for a given hyperfine level, dmf is the molecular frame dipole moment andγF is a geometric g-factor accounting for how the total angular momentum couples to the electricfield (analogous to the magnetic g-factor for an external magnetic field) [45]:γF =F (F + 1) + J(J + 1) − I(I + 1).
2F (F + 1)J(J + 1)

(7.22)For F = 3/2 and 1/2, γF = 1/3 and 2/3, respectively.
Fig. 7.8a shows the spectrum of Stark-shifted levels taken by scanning the 986.4 nm laser
with a rotating bias electric field of 16 V/cm present. As expected from ES being proportional tomF Ω, the two hyperfine levels F = 3/2 and 1/2 yield four and two Stark-split levels, respectively.
However, the Stark levels on the red-detuned side of the hyperfine level tend to be diminished inintensity relative to the blue-detuned side. This is because the rotating field is ramped back down
to zero shortly before firing the photodissociation laser and ejecting the ions from the trap, sothat the large rotating field will not cause the ejected ions to be deflected away from the MCP
detector. The ramping down of the electric field adiabatically transforms the mF levels from statesof good Ω back to states of good parity. On the other hand, the photodissociation laser is tuned
to resonance with the [35.97]Ω′ = 0(J ′ = 1) ← 3 ∆1 (J = 1) transition. Since the upper Ω′ = 0′

state has no Ω-doubling, each rotational level has a fixed parity (-1)J , so parity selection rules
dictate that only the 3 ∆1 |+i levels can make a transition to the excited (J ′ = 1) |−i level. The
intensities of the blue-detuned Stark levels are non-zero because the residual trapping fields induce
a small amount of mixing between the |+i and |−i levels. Based on the above explanation, we
would expect that if we repeated the Stark spectroscopy with the bias electric field ramped down
but with the photodissociation laser tuned to access the (J ′ = 2) |+i excited state, parity selection
rules would similarly cause the red-detuned Stark levels to be diminished in intensity comparedto the blue-detuned ones. Indeed, this prediction matched the intensities of Stark levels detectedusing a R(1) photodissociation line as shown in Fig. 7.8b.
To measure equal intensities for the Stark-shifted levels on both sides of a given hyperfine
level, we carried out the Stark spectroscopy with the rotating bias field ramped down at a later

145

(a)

D1, J = 1

3

J=2

+

J=1

-

Q(1)

R(1)

F=1/2

[35.97]W’=0

-

+

-

F=3/2

+
Photodissociation
pulse|erot|(b)2

Hf counts

Time

1.5

F = 1/2

F = 3/2

Q(1) dissociation

1

+

0.5
0
-0.5

Hf counts

4 R(1) dissociation
3
2

+

(c)

1
0
-80

-60

-40

-20

0

20

40

Two-photon detuning δ (MHz)Figure 7.8: (a) Spectroscopy of the Stark-shifted mF Ω levels in the 3 ∆1 (J = 1) level with arotating bias electric field. The F = 1/2 and 3/2 levels split into two and four levels, respectively.
(a) The rotating field magnitude is always ramped down to zero before the photodissociation
laser pulse is applied, such that the Stark levels are transformed back to states of good parity.
The photodissociation laser can be tuned to either a (b) Q(1) or a (c) R(1) transition. For theQ(1)(R(1)) dissociation transition, detection of the |−i (|+i) parity states is less efficient.

146time, chosen to be large enough to mix states of opposite parity but small enough to not induce
a large deflection kick on the ions when they are ejected. The Stark spectrum was then measured
with three different bias field magnitudes: 22.4 V/cm, 16 V/cm and 8 V/cm (Fig. 7.9a–c). The
bias electric field magnitudes are determined from numerical calculations in SIMION. In accordancewith Eq. (7.21), the Stark levels grew farther apart with larger electric fields. However, at large
enough electric fields such that the Stark splitting between adjacent levels of a single hyperfine levelis comparable to the hyperfine splitting, the ||mF | = 1/2i states for each hyperfine level will start
to mix, and the Stark splittings are modified to give:1
3
E S (F = , mF Ω = ± )
2
2 s





2
dmf Erot
dmf Erot 2
dmf Erot
1
1
=
∓ EHF
+ EF = 3
EHF ∓−+2(7.23a)
2
2
2
2
6
3
1
1
E S (F = , mF Ω = ± )
2
2
s




2
dmf Erot
dmf Erot 2
dmf Erot
1
1
=
∓ EHF
+ EF = 1 (7.23b)+2−EHF ∓
+
2
2
2
2
6
3
(Note that the original appearance of these equations in [45] had some typographical errors, whichhave now been fixed in this thesis.) The |mF | = 3/2 stretch states remain unperturbed by thehyperfine mixing. Fig. 7.9d is a plot contrasting the linear Stark splittings given by Eq. (7.21)(dashed lines) against the Stark shifts accounting for the mixing between hyperfine levels as described by Eq.(7.23) (solid lines). The measured Stark spectra peak positions from Figs. 7.9a–c
are also plotted as a function of bias electric field magnitude in Fig. 7.9d, and are shown to follow
the solid curves, especially at larger electric fields. Using Eq. (7.23), we determined the molecular
frame dipole moment of HfF+ in the 3 ∆1 state to be 1.54(1) e a0 , which turned out to be very
close to the value of 1.50 e a0 predicted by Petrov et. al. [63].
With the ability to populate two 3 ∆1 (ν = 0) |F, J, mF , Ωi quantum states by tuning theRaman transfer lasers to a particular two-photon resonance, we are now poised to consider various
schemes for implementing Ramsey spectroscopy to measure the eEDM-sensitive transition.

147

F = 1/2

Hf+ counts(a)

Hf+ counts(b)

Hf+ counts(c)F = 3/2

4

22.4 V/cm
3
2
1
0
4

16.0 V/cm
3
2
1
0
6

4

8.0 V/cm

20|εrot| (V/cm)(d) 25
20
15
10
5
0

−80

−60

−40

−20

0

20

Two−photon detuning δ (MHz)Figure 7.9: Stark spectroscopy of the 3 ∆1 (ν = 0, J = 1) state with a rotating bias field of (a)22.4 V/cm, (b) 16.0 V/cm and (c) 8.0 V/cm/ (d) The Stark-shifted peak positions are plotted
as a function of rotating electric field magnitude as colored dots. The dashed lines are the linear
Stark shifts from Eq. (7.21) and the solid lines are the Stark shifts including perturbation effects
as described in Eq. (7.23).

Chapter 8
Ramsey spectroscopy of the eEDM-sensitive transitions [50]Over the length of this thesis, we have progressed from conducting HfF+ vibronic spectroscopy
with initial theoretical uncertainties of 100 THz to resolving Stark splittings in a given rovibronichyperfine state at the 10 MHz level using a rotating bias field. We have already managed to isolate
and populate only two |mF , Ωi levels by tuning the Raman laser frequencies to access only one of
the Stark manifolds. To measure the eEDM, we need to first measure the energy splitting between
the two |mF , Ωi levels within a Stark manifold using Ramsey spectroscopy, and then repeat thefrequency measurement for the other eEDM-sensitive transition. At this stage, we only need threeremaining experimental tools to perform the Ramsey spectroscopy:(1) a way to prepare the ions in only one of the two |mF , Ωi levels,(2) a magnetic field that is co-rotating with the bias electric field, and(3) a method for imposing a coherence between |mF = +3/2i and |mF = −3/2i.
This chapter1 describes the physics and implementation of Ramsey spectroscopy of trapped
HfF+ molecular ions in rotating bias electric and magnetic fields. The Ramsey spectroscopy, whichis the first demonstration of coherent spectroscopy of trapped ions with a rotating quantization
axis, yields a measurement of the magnetic g-factor for the 3 ∆1 state, which has been previously
estimated to be small but never measured. From the magnetic g-factor data, we obtain a preliminary limit on the eEDM and provide an estimate of the attainable statistical uncertainty for the1

Much of this chapter will be appearing in Reference [50].

149eEDM with current parameters. Finally, this chapter closes with an outlook for the JILA eEDM
experiment.

8.1

3∆1 levels with rotating bias fields

In the presence of a constantly rotating quantization axis, adjacent projections (i.e. ∆m =±1) of an angular momentum onto the quantization axis become mixed as viewed in the laboratory
frame that is outside of the rotating frame. For instance, for a spin-1/2 particle, the eigenstateθ|−zi } as the quantization axis
projections of the spin changes from {|±zi} to {± 21 |zi − cossinθ±1

rotates by an infinitesimal polar angle θ. Similarly, for a constantly rotating bias electric field(which acts as the quantization axis), adjacent mF levels of the 3 ∆1 (ν = 0, J = 1, F = 3/2) state
become mixed. In the case of states |ai and |bi (and similarly, |ci and |di) separated by a three√√photon transition as illustrated in Fig. 8.1a, the eigenstates are {(|ai ± |bi)/ 2} ({(|ci ± |di)/ 2})
under a rotating bias electric field, where the energy splitting ∆ between the eigenstates is givenby∆ ∝ ωefωrot
dmf Erot

3

.

(8.1)

∆ is the same as ω u/ℓ for the case of B = 0. The exponent of 3 in Eq. (8.1) comes from the factthat three photons are needed to couple mF = 3/2 ↔ −3/2, whereas the ωef term is present toprovide a coupling between states of Ω ↔ −Ω, which must also be overcome for the three-photontransition to occur.
So far, the above physics is valid in the absence of a magnetic field. In the presence of amagnetic field co-rotating with the bias electric field, the mF levels can be interchangeably referred
to as either Stark or Zeeman levels. Where there is a magnetic field Brot large enough to provide
a Zeeman shift that can overwhelm the energy splitting ∆, the eigenstates then resume to be{|ai , |bi}. The full spectrum of the levels in the uppermost Stark manifold of the 3 ∆1 (F = 3/2)
state in the presence of rotating electric and magnetic fields is given by the avoided crossing depicted
in Fig. 8.1b, where the asymptote of the avoided crossing is the Zeeman shift for each of the two150
stretch states, ±(3/2)gF µB Brot .
In accordance with Eq. (1.7), the eEDM measurement would then correspond to a Ramsey
spectroscopy measurement of the frequency splitting between the two levels at some finite ±Brot(shown as two vertical arrows in Fig. 8.1b) for both the upper and lower Stark manifolds. Sitting
on the side of a Ramsey fringe at a given time, one can detect a small shift in the frequency (dueto the eEDM) as a shift in fringe position (Fig. 8.1c). However, the ability to sit on the side ofa Ramsey fringe requires knowledge of the Ramsey fringe frequency, or in other words, knowledgeof the spectroscopic constants ∆ and gF defining the avoided crossing, neither of which has been
experimentally determined until this thesis work.
While Eq. (8.1) gives a qualitative understanding for ∆, the g-factor for the 3 ∆1 state canbe estimated as follows [45]:gF = γF ((gL + gr )Λ + (gS + gr )Σ) sign(Ω) − gr J(J + 1) − gI κF ,(8.2)

where gL and gS are the orbital and spin g-factors, and gr and gI are the rotation and nuclear
spin g-factors. gr and gI are small as they are on the order of the ratio of electron mass tomolecular mass, i.e. me /mmol ∼ 10−3 . In the 3 ∆1 state, Λ = ±2 and Σ = ∓1 whereas gL = 1 and
gS = 2 + α/π + O (α/π)2 , such that there is a near cancellation of the orbital and spin magnetic

moments and the overall g-factor becomes very small. On the other hand, spin-orbit mixing, which
is predominant in heavy molecules, may cause the 3 ∆1 state to contain admixtures of other states,
such that the cancellation of the orbital and spin magnetic moments is not as complete, giving

a bigger g-factor. In any case, the relatively small g-factor is one of the chief advantages of the3∆

1 state, because it reduces the sensitivity of the eEDM transitions to stray magnetic fields. An

experimental determination of the g-factor requires the implementation of a rotating magnetic field,
which is described in the following section.

151

D1, n=0, J=1

3

(a)

(b)
1 E

b/d

u/l

E/D

F = 1/2

F = 3/2u, upperStark
manifold{

F- S =-1
n̂
2+

Hf

|bñ

m BB
3g F

d ee
+2

eff

|añ

n̂

Hf

|W = +1ñ

erot B Hfl, lowerStark
manifold

2+

{ F

-

n̂
S = +1|W = -1ñ

e
B - 2d3g Fm B

e

Hf2+
eff

mF = -3/2

-1/2

-

Eb/d
-2

-1

0

1

2

3

3gFmBB/D(c)
Ions(|añ) - Ions(|bñ)

wu(e, B)wl(e, B)S = -1F|W = +1ñ

1/2

Ea/c

n̂

|cñ

|dñ

u/l

u/l

-3

2+

|W = -1ñ

w (B)w (-B)

0-1

F- S =+1

Ea/c

D

Time

3/2

Figure 8.1: (a) (Reproduced from Fig. 1.5) HfF+ energy levels in the 3 ∆1 , ν = 0, J = 1 statein the presence of an external electric and magnetic field, where the eEDM-sensitive transitions
are between states |ai and |bi and between states |ci and |di. (b) In the presence of a rotating
quantization axis, |ai and |bi (similarly, |ci and |di) are coupled to each other and form an avoided
crossing as a function of magnetic field. At the center of the avoided crossing (i.e. no magnetic
field), the eigenstates are equalsuperpositions of the stretch states of the same Stark manifold,√e.g. {|0i , |1i = (|ai ± |bi)/ 2} for the upper Stark pair. The vertical green arrows denote the
eEDM-sensitive transition frequencies. (c) Ramsey fringes measured for the upper (solid) andlower (dashed) Stark manifolds. The eEDM signal is proportional to the amount by which theRamsey fringe moves when sitting on the side of a fringe.

152

8.2

Experimental tools

8.2.1

Rotating magnetic field

To implement a rotating magnetic field, one can imagine running AC currents up and down
the fin electrodes in a way as to create a rotating magnetic field that is aligned parallel or antiparallel to the rotating bias electric field. A simpler approach to mock up Brot is by installinga static radial magnetic field gradient using a pair of anti-Helmholtz coils: Fig. 8.2a shows a 3dimensional view of the coils and B field lines relative to the fin electrodes, and Fig. 8.2b depicts
the top view of the ion trap with the radial B field gradient. To understand how the static B
field gradient, in combination with the rotating electric field, gives rise to a rotating magnetic
field, consider the magnetic field lines sampled by a HfF+ ion undergoing circular micromotion at
the rotating field frequency ωrot as illustrated in Fig. 8.2b. At time 0, E~rot points along x̂ andsince ~rrot ∝ −E~rot , the molecular ion starts out on the left side of the micromotion circle. The~
magnetic field sampled by the molecular ion points in the direction −B(rrot )x̂ + Bstatic (R)ŷ,
where
B(rrot ) is the magnitude of magnetic field at the radius of circular micromotion rrot from the trap
~ is the magnetic field at the center of the micromotion circle (R).
~center. Bstatic (R)A quarter
rotation cycle later, E~rot points along ŷ while the magnetic field sampled by the ion points along~(−B(rrot ) + Bstatic (R))ŷ.
Over the course of a rotation cycle, then, the magnetic field experienced~
by the ions can be decomposed into a spatially-dependent but time-invariant component Bstatic (R)~rot (t) = ∇B
~ · ~rrot that rotates with the bias electric field, either
and a time-varying component B
in phase or 180◦ out of phase (depending on whether the magnetic field lines point radially inward~ static (R)~ is a function of theor outward). By definition, Brot is positive if it lies parallel to Erot . B
ions’ secular displacement within the trapping volume, but for any given instant in time, all the~ static (R)~ across the ion cloud is of little concern,
ions experience identical Brot . The variation in B
since the rotating quantization axis makes us primarily sensitive to the rotating component of themagnetic field.
Fig. 8.2c shows a photograph of the anti-Helmholtz coils installed to produce the magnetic

153
field gradient. Each coil (mean radius 135.9 mm) is made by winding 3 layers of 13 turns of 2.66 mmdiameter square copper wire. The anti-Helmholtz pair produces a radial gradient of 0.08254 G/cm
for 1 A of current. The coils are driven by a Kepco BOP 20-20M bipolar power supply, whose
output can be externally controlled by an analog input voltage to provide up to ±20 A of current.
As shown in Fig. 8.2c, the coils are situated outside the trap chamber, which means that timevarying changes to the magnetic fields are impeded by eddy currents in the large aluminum mirrors
originally designed for fluorescence collection in the trap. The eddy currents dissipate on the timescale of 20 ms (Fig. 8.2d), which means that any ramps in the magnetic coil currents need to takemuch longer than 20 ms so that the actual trap fields can follow the current drive.

8.2.2

Optical pumping

In order to perform Ramsey spectroscopy, the ions must be initialized in only one of thetwo |mF , Ωi levels. As explained in Chapter 7, the usual atomic physics trick of preferentially
populating the molecular ions in one of the two stretch states using circularly-polarized light does
not work due to the combination of the quantization axis rotating and the need for Raman transfer
lasers to propagate perpendicular to the plane of rotation. The following scheme, however, does
work: after the Raman lasers populate the ions in both |mF , Ωi levels of a Stark manifold, acircularly-polarized optical pumping laser (henceforth referred to as the ‘depletion’ laser) tuned toresonance with the 3 Π0+ (J ′ = 1) ← 3 ∆1 (J = 1) transition is used to deplete the ions in one of
the two stretch states. The depletion laser is aligned along the same beam path as the ionizationand dissociation lasers, and is stroboscopically turned on with a duty cycle of 20% whenever thequantization axis lies parallel to the direction of laser propagation. The depletion laser is picked offfrom the 986 nm transfer laser and sent through two acousto-optic modulators as intensity switches
that are aligned to ensure no depletion laser light is incident on the ions when the quantization axis
has rotated by 180◦ . Due to the reduced depletion laser intensity and large Doppler shift associatedwith vrot , as many as 250 rotation cycles may be needed to fully deplete the ions from one of thestretch states (say, |bi), leaving the ions in only |ai. To change the handedness of the depletion

154

Current in antiHelmholtz coils

(a)

(b)

Y

wrot

Z

ˆ
erot = erot (cos(wrott) xˆ + sin(wrott) y)
X
Z
HfF+

X
Y

B field
lines

B field
lines

B field lines in
1 rotation cycle:
Brot

Bstatic

Current+

Anti-Helmholtz coils

0
(d)

Large
Al
mirrors

p/2

p

3p/2

wrott

2x100
Response amplitude

(c)

0

10

3x10

-1

-1

10

0

1

10
10
Frequency (Hz)2

10

Figure 8.2: (a) 3-dimensional schematic of the fin electrodes and anti-Helmholtz magnetic fieldcoils, which create a radial magnetic field gradient shown by the gray arrows. (b) Top view of theion trap showing the fin electrodes and magnetic field lines in the plane of rotation. A molecular ion
undergoes circular micromotion at ωrot and samples the magnetic field lines that can be decomposed
into Brot (t) + Bstatic . For the case depicted with the B field lines pointing outwards radially, Brot
is 180◦ out of phase from Erot , i.e. Brot < 0. (c) Photograph of the anti-Helmholtz coils. (d) The
response of the magnetic field gradient in the trap center to any changes in the coil current isimpeded by eddy currents in the large aluminum trap mirrors on the time scale of 20 ms.

155
laser polarization, one can simply offset the timing of the depletion laser pulses such that the laser
light is only present when the quantization axis is anti-aligned to the direction of depletion laser
polarization. In the rest of this chapter, the sequence of 250 depletion pulses (or however many areneeded for full depletion) is referred to as a ‘depletion laser strobe-sequence’.

8.3

Ramsey spectroscopy at B = 0
We now embark on experimentally mapping out the avoided crossing depicted in Fig. 8.1b.

The first step is to understand the avoided crossing splitting at the point of closest approach ∆ byperforming Ramsey time-of-flight spectroscopy in the absence of any magnetic fields. The Ramsey
sequence is as follows: after populating ions in a single Stark manifold (say, both |ai and |bi
incoherently in the upper Stark manifold u), the ions in state |bi are optically pumped away witha σ + -polarized depletion laser strobe-sequence. The remaining ions in |ai can then be expressed as√√
populating a superposition of the two eigenstates {|0i , |1i ≡ (|ai±|bi)/ 2}, i.e. |ai = (|0i+|1i)/ 2.
In other words, the depletion strobe-sequence is equivalent to performing a π/2-pulse on the ions,the physics of which is analogous to the following: a beam of unpolarized light, sent through agedanken σ + -polarizer, becomes σ + -polarized, which is also a linear combination of horizontal andvertical linear polarizations. A variable wait time T ensues, during which the relative phase betweenuthe states |0i and |1i freely evolves as e−iω T , due to |0i and |1i being the eigenstates under therotating electric and magnetic fields. The π/2-pulse is then applied again with a σ + -polarized
depletion laser and the Hf+ ions detected upon firing the dissociation laser only come from thoseremaining in state |ai. The number of ions remaining in |ai is related to the argument of thefree evolution phase as follows: at ω u T = 2nπ (where n is an integer), there is no change in theion number for |ai between the first and second π/2-pulse. Conversely, after ω u T = (2n + 1)π,
all the ions initially in |ai would have been transferred into |bi, giving maximal depletion signal
with the second π/2-pulse. In general, the change in ion signal in |ai between the first and second
π/2-pulse is proportional to (1 − cos(ω u T )). The above Ramsey sequence can be repeated using
σ − -polarized light for the second π/2-pulse, which makes the dissociation laser sensitive to a change

156
in ion population in state |bi. The difference between the two chops (differing in the helicity ofthe second π/2-pulse) then provides the relative change in ion population between states |ai and|bi, which is proportional to the relative phase between the two states accumulated during T . To
normalize for any drifts in ion number at a given wait time T , the ion number is also recorded
without any π/2 pulses applied. The combination of these chops give the fractional difference inion population between states |ai and |bi as a function of the free evolution time T , and is shown
as a Ramsey fringe in Fig. 8.3b.
Fig. 8.3c shows the zero-magnetic-field Ramsey fringe frequencies plotted as a function ofrotating bias electric field magnitude for both Stark manifolds {|ai , |bi} and {|ci , |di}. For a
3 (Fig. 8.3d),
given Erot , the average of the two fringe frequencies is inversely proportional to Erotas predicted by Eq. (8.1) for a three-photon transition. On the other hand, the slight frequency
difference δ∆ between the two Stark manifolds comes from interactions with the F ′ = 1/2 hyperfine
level, i.e. the upper Stark manifold is further repelled from the F ′ = 1/2 levels than the lower Stark
manifold. Since the mF = ±3/2 states are connected to the m′F = ±1/2 states in the F ′ = 1/2
manifold through a one-photon transition, the frequency difference δ∆ is proportional to the ratioof the Stark shift to the hyperfine energy difference ((dmf Erot )/EHF )1 , and akin to the expressionfor ∆, δ∆ is also proportional to 1/(dmf Erot )3 . More precisely, perturbation theory on the Hilbert
space of 12 |F, mF , Ωi sub-levels in the 3 ∆1 (J = 1) rotational state yields the following expressions
[54]:
∆ =
δ∆ =


3

ωrot
1 ℓ
u
∆ + ∆ = 27ωef,2
dmf Erot

3 

 81
dmf Erot
ωrot
1 ℓ
u
∆ −∆ =
ωef.
2
8
dmf Erot
EHF

(8.3)
(8.4)

The lines shown in Fig. 8.3c–e come from a simultaneous fit to ∆, δ∆, ∆ℓ and ∆u using Eqs. (8.3)–(8.4), and the data gives good agreement with perturbation theory.

The sole fit parameter,ωef /(2π), is determined to be 830(50) kHz, which is a more precise value for the zero-field splitting
between states of opposite parity compared to its previous estimate of 740 kHz, where the latterhas been obtained by extrapolating from ωef /(2π) observed in high-lying rotational levels of HfF+

157
in a discharge tube [16].

8.4

Ramsey spectroscopy at B 6= 0
Having understood the avoided crossing splitting at the point of closest approach, we now

turn to measuring gF . In principle, gF can be determined by performing Ramsey spectroscopy inthe same way as described in Section 8.3 but with a finite magnetic field gradient applied throughout
the Ramsey sequence. However, as Brot gets larger, the Ramsey fringe contrast decreases because
the eigenstates at larger Brot are more similar to the mF stretch states and the depletion laser
strobe-sequence behaves less like a π/2-pulse. With a lower fringe contrast, the fringe frequency ismore difficult to determine.
There is a simple modification to the Ramsey sequence in Section 8.3 that can still yield
fringes of relatively high contrast. Starting with no magnetic field, the depletion laser strobesequence is used to create an equal superposition of |ai and |bi. The magnetic field gradient is thenramped on, held a finite value for the free evolution time T , and finally ramped back down to zerofor the second depletion laser strobe-sequence acting as the π/2-pulse. The main problem with themagnetic field ramps is the fact that eddy currents in the ion trap occur on a time scale significant
to the coherence time of the Ramsey fringes. In order for the magnetic field at the trap center toreliably follow the expected field values from driving currents, the magnetic field ramps then haveto occur on the time scale slower than that of the eddy currents, which means that after accounting
for two magnetic field ramps, there is hardly any free evolution time that one can afford to wait
for before the Ramsey fringe contrast diminishes due to decoherence. In a future iteration of theeEDM experiment, designed to avoid large eddy currents (e.g. by removing the aluminum mirrors
from the ion trap), one can revisit this idea of ramping the magnetic field, in which case one only
has to be careful to account for the ramps affecting the initial phase of the Ramsey fringe.
Another method of performing the Ramsey π/2-pulses uses the fact that the avoided crossing
splitting ∆ depends strongly on the rotating electric field magnitude. Fig. 8.4a shows the avoided
crossing for two values of Erot . The Ramsey sequence is carried out as follows (Fig. 8.4b): at a given

158

Strobed s
depletionp/2
Strobed s
depletion+tτ = 100(30) ms

100
50
0

0.5

6

8

10

e (V/cm)

12

rot

(d)

100

0

50

100

150

Time T (ms)

200

u

0

1

2

-3

3 x10

1/erot3 (cm3/V3)

25
20
15
10
5

l

-1

l

u

-0.5

(e)

200

D /2 (Hz)(2pD - 2p)

0

D /2 (Hz)(2pD + 2p)

Fractional
population difference

1

Dl/2p
Du/2p

150

Spin precession
time T
(b)

200

(c)
+

D/2p (Hz)

p/2

(a)

0

0.01 0.02

1/erot2 (cm2/V2)

Figure 8.3: (a) Ramsey sequence performed to measure the zero-B-field splitting ∆, where thedepletion laser strobe-sequence acts as a π/2-pulse. (b) Sample Ramsey fringe recorded at B = 0,
where the fractional population difference (Na − Nb )/(Na + Nb ) is plotted as a function of the freeevolution time T . The fit fringe frequency is ∆ = (2π)24.5(5) Hz. (c) Plot of ∆/(2π) as a functionof Erot for both the upper (red crosses) and lower (blue dots) Stark manifolds. (d) The mean
3 , which is in agreement withvalue of ∆ for the two Stark manifolds is inversely proportional to Erot
Eq. (8.3). (e) The difference in ∆ for the two Stark manifolds follows that predicted by Eq. (8.4).
The lines in (c–e) are simultaneous fits of the data to Eqs. (8.3) and (8.4), with the zero-electric-field
splitting ωef as the only fit parameter.

159
applied magnetic field gradient, we first populate, say, the upper Stark manifold, and then apply
a σ + -polarized depletion laser strobe-sequence such that the ions are only left in state |ai. The
rotating electric field magnitude is subsequently jumped down to a lower value, which increases the
avoided crossing splitting so that the ions in state |ai are projected onto a basis of eigenstates thatare nearly equal superpositions of |ai and |bi. After waiting for a short time, the rotating electricfield magnitude is increased back to its original value, such that the total duration of any changes
in the electric field corresponds to a π/2-pulse. The ions are allowed to evolve freely in time T , andthe same π/2-pulse is repeated to project the ions back into either state |ai or |bi, which can beread out using the circularly polarized depletion laser and dissociating the remaining HfF+ ions.
The Ramsey fringe frequencies obtained from applying the above electric-field-ramp sequence
are plotted for several different magnetic field gradients in Fig. 8.4c. The avoided crossing is mappedout for both the upper and lower Stark manifolds, and the data for each Stark manifold is fit to
the following function:
ω u/ℓ
2π

s

=2



∆u/ℓ
2(2π)

2

+



2
3
u/ℓ
u/ℓ
µB gF (rrot · ∇B − Boffset ) ,
2

(8.5)

where the radius of circular micromotion rrot = 0.22 mm for a rotating electric field magnitudeof 11.6 V/cm during the free evolution wait time. The second order Zeeman effect is negligible
at the level of . 10−2 compared to the linear Zeeman effect for our experimental parameters.
The fit parameters yielded ∆u = 25(1) Hz and ∆ℓ = 36(1) Hz, which are in good agreementuwith that expected from Eqs. (8.3)–(8.4). The magnetic field offsets fit to Boffset= 0.15(11) mGℓand Boffset= 0.02(9) mG, although lower offsets have been obtained when considering a subset ofRamsey fringe data taken within a short time window of each other. One source of contribution to
Boffset comes from currents driven up and down the fin electrodes to provide the rotating voltages:
Irot = Vrot ωrot Cfin ,Boffset = 3µ0 Irot,
2πrfin

(8.6)
(8.7)

where Irot is the current for a single fin, Vrot is the amplitude of the rotating voltage, Cfin is thecapacitance between two oppositely placed fin electrodes and rfin = 4 cm is the distance between

160
the trap center and any given fin. The factor of 3 in Eq. (8.7) is a geometrical factor accounting forthe fact that the six fin electrodes are spaced 60◦ apart and adjacent fins are driven out of phaseby 60◦ . The total capacitance of a single fin (without its SHV-feedthroughs) is measured within
the assembled ion trap to be 32 pF, which is likely to be dominated by the capacitance between
the fin and aluminum mirror at the two points of closest approach. Using an estimated capacitanceof 5 pF between opposite fins, for a rotating electric field of 11.6 V/cm or Vrot = 75 V, Boffset is
calculated to be 0.089 mG, which is about the same as that measured. This effort should be quite
stable and thus readily cancelled.
Finally, the fit of the avoided crossing yields the magnetic g-factors |gFu | = 0.00306(1) and|gFℓ | = 0.00305(1). Both magnetic g-factors are measured to be very small and within a factorof two of that predicted by Eq. (8.2), which means that there is little state mixing from otherlevels into the 3 ∆1 state. The reported error on the g-factors (δgF = 10−5 ) is only the statisticalerror. We have yet to estimate the systematic error on gF , which is likely to be dominated by theuncertainty on the value of Erot . The upper and lower Stark manifolds are expected to exhibit aslight difference in gF due to three contributions, which are briefly listed as the following [45]:(1) Centrifugal distortion terms in the zero-electric-field Hamiltonian, giving a parity-dependent
gF ,(2) Perturbations to the |mF , Ωi levels from Erot mixing adjacent rotational levels, in whichcase one gets
δgF =9dmf Erot
gF ,
40Be

and

(8.8)

(3) Perturbations to the |mF , Ωi levels from the rotating quantization axis coupling mF levels
between the two hyperfine states (i.e. between |F = 3/2, mF = ±1/2i and|F ′ = 1/2, m′F = ±1/2i):
δgF =

√

2
ωrot
gF .
γF2 =3/2 dmf Erot EHF

6

(8.9)

Since there is an electric field of 11.6 V/cm applied, the first contribution is negligible. The second
and third contributions are calculated to be 1.8 × 10−6 and 4.1 × 10−6 respectively, which are so far

161
in agreement with the (crude) measured difference. One should note that by mapping out the wholeavoided crossing as shown in Fig. 8.4c, neither the difference in g-factors nor Boffset is measured ina manner optimal for high precision. Instead, one should chop quickly between four sets of Ramsey
fringes taken at some finite ±∇B and for both the upper and lower Stark manifolds in order todetermine δgF and Boffset more precisely.

8.5

Sign of magnetic g-factor
So far, the application of Ramsey spectroscopy to determine the magnetic g-factor only yields

the magnitude of gF , but not its overall sign: regardless of whether the ions in |ai (or |ci) absorb
from or emit energy into the rotating magnetic field, the cos(ω u T ) signal remains unchanged. The
sign of gF is important especially if a non-zero electron EDM has been measured, as it is also related
to the sign of the non-zero eEDM. Even if a finite eEDM has not yet been measured, determining
the sign of gF involves a cute piece of physics that is not necessarily encountered in many physics
experiments: Berry’s phase. One may think that Berry’s phase, which would add a systematic shift
to the eEDM-sensitive transitions, is unavoidable for our experiment due to the constant rotationof trapped molecular ions. The demonstration of our understanding of Berry’s phase through anexperiment such as measuring the sign of the g-factor is therefore a fantastic reason on its own toperform such an experiment!
To understand how Berry’s phase may be used to determine the sign of gF , let us first take~ that has been tilted
a step back and revisit the Hamiltonian with a rotating quantization axis F
away from the plane of rotation by an angle α = (π/2) − θ (Fig. 8.5a) [45, 57]:
Hdressed = H0 − d~mf · E~rot + Hrot ,(8.10)

where Hrot = −ωrot (cos(θ)Fz − sin(θ)Fx ) .

(8.11)

θ is the polar angle, whereas Fz and Fx are the projections of the quantization axis onto the ẑ
and x̂ axes. The Berry’s phase accumulated from the tilt of the quantization axis away from the

162

(a)

erot
7 V/cm
12 V/cm(b)

Strobed s+

Strobed s+
depletion|erot| depletion

Spin precession
time T

p/2

p/2

Frequency (Hz)Frequency (Hz)

Time

(c)

600

|gl| = 0.00305(1)
400
200
0
600

u

|g | = 0.00306(1)
400
200
0
-2

-1

0

1

2

ÑB (G/cm)

Figure 8.4: (a) Theory curves for the avoided crossing as a function of the rotating magnetic field(mocked up using ∇B), plotted for two different values of Erot . (b) Ramsey sequence performed tomeasure the magnetic g-factor. The π/2-pulses are ramps in Erot ,√which can change the eigenstate
at some finite magnetic field from, say, ≈ |ai to ≈ (|ai − |bi)/ 2. (c) The avoided crossing is
experimentally mapped out for both the lower (blue dots) and upper (red crosses) Stark manifolds.
The slopes of the avoided crossing give |gFℓ | = 0.00305(1) and |gFu | = 0.00306(1).

163
horizontal plane of rotation then gives rise to an energy shift
EBerry = −mF ωrot sin(α) ≈ −mF ωrot α .

(8.12)For HfF+ ions confined to the plane of rotation, EBerry = 0. However, the trapped ions also undergo
axial oscillations, such that the quantization axis (electric field) can be tipped away from the planeof rotation, introducing a Berry’s phase. Considering only states |ai and |bi and ignoring any
contributions to their energies from an eEDM, the Hamiltonian in the state basis {|ai , |bi} thenbecomes




H =

ωmax
3
2 gF µB Brot + 2 cos(ωz t)

∆
2

∆
2

− 23 gF µB Brot − ωmax
2 cos(ωz t)




,

(8.13)

where ωmax = −mF ωrot (Ez,max /Erot ) is the Berry’s phase picked up from the tilt of the quantization
axis (Ez,max /Erot ) and where Ez,max is the maximum axial electric field experienced by the ions as
they oscillate away from the plane of rotation (z = 0).
For a cloud of ions oscillating about the z = 0 plane with a random initial phase in the axial
direction, the Berry’s phase accumulated by some ions oscillating above the plane of rotation cancels
out that accumulated by ions oscillating below the plane of rotation, such that the overall Berry’s
phase is zero. On the other hand, if the entire ion cloud is oscillating, say, in the region z > 0, theions can accumulate an overall Berry’s phase, which, depending on the relative orientations of thequantization axis (electric field) and the magnetic field, can shift state |ai up or down in addition
to the Zeeman shift (with the opposite Berry’s phase shift for |bi). For ωmax cos(ωz t) > 0, the twoterms dominating the energies of states |ai and |bi (i.e. (3/2)gF µB B rot versus (ωmax /2) cos(ωz t))
will have the same sign if gF Brot > 0, so that the two levels are further split apart with the Berry’s
energy shift (and vice versa if gF Brot < 0).
Experimentally, to determine the sign of gF , we carried out the same Ramsey sequence as
described in Section 8.4 but with an additional ‘kick’ applied to the ions along the axial direction
before performing the first π/2-pulse. The axial frequency was lowered to (2π)0.8 kHz, such thatthe ions would be moving in only the upper half region z > 0 in the first 625 µs. According to
Eq. (8.13), such an upward kick to the ions yields ωmax > 0, and the accumulated Berry’s phase

164
would shift the Ramsey fringe frequency to be larger or smaller depending on the sign of gF . The
experiment can then be repeated with the ions kicked down into the region z < 0 to make surethat the Ramsey fringe shifts in the opposite direction compared to the chop with the upward kick.
Fig. 8.5d shows the Ramsey fringes obtained with the ions kicked into z > 0 (blue dots) and also
into z < 0 (red crosses), for the case where Brot > 0. Relating the fringe phase shift observed in
the first 625 µs (shaded region on the plot) to Eq. (8.13), one can therefore determine the signof the g-factor.2

As an additional sanity check, the two chops are repeated, this time with an

outward radial magnetic field gradient, i.e. Brot < 0. As expected, the Ramsey fringe phase shifts
are now reversed compared to that plotted in Fig. 8.5d for the kicks in the two axial directions, as
the relative sign between gF Brot and ωmax cos(ωz t) has flipped.
One should note that there is at least one other alternative method for measuring the sign of
gF : one can instead measure the Stark splitting between adjacent mF levels in both the presence
and absence of a rotating magnetic field, by first populating state |ai using the Raman transfer
lasers and depletion strobe-sequence, and then applying RF photons to couple |ai to its adjacentstate |F = 3/2, mF = 1/2, Ω = −1i. For Erot = 16 V/cm, the Stark splitting is 10.5 MHz, whichmeans that to determine the sign of gF by recording a 100 Hz shift on the RF transition, Erot needs
to be stable to 10−5 , which is plausible but no mean feat to achieve.

8.6

A preliminary eEDM measurement and some implications for sensitivity
to systematics
Returning to the avoided crossing mapped out in Section 8.4, we can combine the Ramsey

fringe frequencies recorded at some finite ±∇B and for both the upper and lower Stark manifolds
as the terms in the ‘four-way chop’ described in Eq. (1.7) to give a preliminary limit on theeEDM: |de | < 10−25 e cm. A serious measurement of the eEDM would involve sitting on the sideof a Ramsey fringe and looking at a shift of the Ramsey fringe position for any given chop, as
2

At the time of thesis submission, we still have not yet reached a consensus on the sign of the g-factor. However,
the method of determining the sign by kicking the ions and observing the subsequent Ramsey fringe phase shift
remains on a fairly solid foundation. The final consensus on the sign of the g-factor will be reported in Reference
[50].

165

(a)

(b)

z

A ~ 2p(1-a)

gFBrot < 0

gFBrot > 0y|mF = +3/2ñ

F

wrot

a = p/2 - qx|mF = -3/2ñ

|mF = -3/2ñ
|mF = +3/2ñ

wmaxcos(wzt)(c)

Fractional
population difference

0

1

0

erot
Brot

wmaxcos(wzt)

ez
erot

Downwards
kick

0.5
Upwards
kick

0

erot
ez

0

1

2

3

Time T (ms)~ away from
Figure 8.5: (a) (Adapted from [45]) The tipping of the rotating quantization axis F
the plane of rotation by the angle α introduces a non-zero Berry’s phase that is proportional to
the solid angle A. (b) If gF Brot > 0, the |mF = ±3/2i levels in the absence of Berry’s phase are
Zeeman-shifted so that |mF = 3/2i lies above |mF = −3/2i in energy. With Berry’s phase providing
ωmax cos(ωz t) > 0, however, the two Zeeman levels are split further apart. Conversely, if gF Brot < 0,
the |mF = −3/2i level is higher in energy, but with Berry’s phase giving ωmax cos(ωz t) > 0, the|mF = −3/2i level is lowered slightly whereas the |mF = 3/2i state is raised, causing the two
Zeeman levels to have a smaller splitting. (d) Ramsey fringes recorded with the molecular ions
undergoing a finite Berry’s phase as they are either kicked upwards (blue dots) or downwards (redcrosses) from the plane of rotation. The shaded region corresponds to half an axial trap oscillation,
which is also the time over which the ions are only in the z > 0 (or z < 0) region and where thephase shifts of the Ramsey fringes are of interest. This data is recorded with Brot > 0, such thatthe observed phase shifts for the two kicks yield gF < 0.

166
opposed to recording the entire fringe. For imperfect π/2-pulses, the initial phase of the Ramsey
fringe may be less well-understood, which means that in addition to sitting on only a side of
the Ramsey fringe, we may also have to measure the initial phase of the fringe. These chops
would have to be performed with a ‘blind’ offset added to each frequency measurement so thatthe experimenters will not be biased towards a particular eEDM value [36]. The final reported
eEDM value is then given by the offset combined with the statistical uncertainty and systematic
uncertainty: de = (doffset± δdstat± δdsystee ).
e
As mentioned at the beginning of this thesis, δdstat
is inversely proportional to the figuree
of-merit, which is in turn proportional to the effective electric field, coherence time and squareroot of the number of spin-flip transitions detected. The potentially long coherence time offeredby trapped molecular ions over neutral molecules is one of the chief advantages of the JILA eEDM
experiment. In Fig. 8.6a, we show that we can currently achieve coherence times longer than
150 ms, which is approximately two orders of magnitude higher than all other molecule eEDM
experiments that offer a similarly large effective electric field. The long coherence time of 150 ms,
combined with Eeff = 24 GV/cm and 4 spin-flips detected per shot at a repetition rate of 1 Hz, puts√
= 2.2× 10−28 e cm/ day. Further, the 100-times higher
our present statistical uncertainty at δdstateresolution provided by the narrower spin-flip transition linewidth means that we are less sensitive tosystematic effects that distort the lineshape. The source of decoherence beyond 150 ms is presently
a topic of investigation, and preliminary studies point to ion-ion interactions as a plausible factor,
although a more detailed study needs to be performed to sort through the different decoherence
sources. The ultimate goal we wish to achieve for the coherence time is the rovibronic lifetime of
the 3 ∆1 (ν = 0, J = 1) state, which has been measured to be as long as 1.6(4) s (Fig. 8.6b). With alonger coherence time, both our statistical uncertainty and sensitivity to systematics can be further
lowered.
Returning to the (coarse) measurements of δ∆ and δgF obtained in Sections 8.3 and 8.4, we
examine the implications of these quantities for potential systematics in an eEDM measurement.
As explained in Reference [45], the most important contributions to a systematic effect that could

167
survive the four-way chop are quantities that influence ω u and ω ℓ separately, e.g. δgF and δ∆.
Firstly, for a given δgF , a systematic shift from any stray rotating magnetic fields or magnetic field
gradients would be reduced by δgF /gF after the four-way chop:
u/ℓ

stray
stray
stray
± 2de Eeff ,) + ω u/ℓ (Erot , −Brot + Brot
) = 6gF µB Brot
ω u/ℓ (Erot , Brot + Brot

i
stray
stray
ω u (Erot , Brot + Brot
) + ω u (Erot , −Brot + Brot
)
h
i
stray
stray
− ω ℓ (Erot , Brot + Brot
) + ω ℓ (Erot , −Brot + Brot)

(8.14)hstray= 12δgF µB Brot
+ 4de Eeff .

(8.15)

stray
Further, Brot
can be reduced by compensating for it with a non-chopped rotating magnetic fieldshim . The combination of B shim and our theoretical values for δg is expected to put our eEDM
Brot
F
rot

systematic sensitivity below 10−28 e cm. Secondly, δ∆ gives rise to a systematic shift if a chop in
Brot causes a change in Erot by δEchop :[ω u (Erot + δEchop , Brot ) − ω u (Erot − δEchop , −Brot )]hi− ω ℓ (Erot + δEchop , Brot ) − ω ℓ (Erot − δEchop , −Brot )δ∆ηδEchop∆
dmf Erot≈3
ηδEchop .
EHF=8(8.16)

where η is the analog of the sensitivity of ω u/ℓ to Erot as gF is to Brot :η u/ℓ ≡(∆u/ℓ )2
∂ω u/ℓ=.
0u/ℓ∂Erot Erot ,BrotgF µB Brot Erot

(8.17)For Erot = 11.6 V/cm, Brot = 15 mG and a plausible value of δEchop = 100 µV/cm, η =(2π)1.6 Hz/(V/cm) and the remainder systematic shift given by Eq. (8.16) is estimated to be(2π)0.25 mHz, which is at the 5 × 10−30 e cm level.

8.7

Conclusions and outlook
By the end of this thesis, we have developed all the techniques required to perform an eEDM

measurement: the quantum state preparation is accomplished by first autoionizing neutral HfF

Fractional
population difference

168

1

(a)

τ = 190(60) ms

0.5
0
−0.5
−1

0

50

100

150

200

8

3

τ ( ∆1) = 1.6(4) s

6

3

1

(b)

Dissociated ∆ , J=1 IonsFree evolution time T (ms)

4
2
0

0

1

2

3

Time (s)Figure 8.6: (a) The coherence time for the Ramsey spectroscopic measurement of an eEDM-sensitivetransition frequency is presently limited to about 200 ms. (b) Decay of the number of dissociated3 ∆ (ν = 0, J = 1) HfF+ ions as a function of trap time. The coherence time is not limited by1
the rovibronic lifetime of the 3 ∆1 (ν = 0, J = 1) state, which we have measured to be as long as
1.6(4) s.

169
molecules into the true electronic ground state 1 Σ+ , and then performing a Raman transfer of the
HfF+ molecular ions into the desired 3 ∆1 quantum states, while the efficient state detection isachieved by rotational-state-resolved photodissociation. In the meantime, the ions remain trappedin a RF Paul trap of a novel design and are subject to rotating bias electric and magnetic fields.
The rotating electric bias field is unique to our ion trap experiment and has not been utilized in any
other RF Paul traps. We have provided the first demonstration of coherent Ramsey spectroscopy ofions in a rotating bias field, where the π/2-Ramsey-pulses are implemented by ramping the rotating
electric field.
For the eEDM measurement, the combination of Ramsey fringes taken at opposite magnetic
fields and with different sublevels of the 3 ∆1 state gives |de | < 10−25 e cm, and our present
numbers for the coherence time and spin-flip transitions detected put our statistical sensitivity√−28 e cm/ day. The sources of decoherence remain to be understood and theat δd1σe < 2.2 × 10
coherence time to be improved, after which a full systematic evaluation of the eEDM will be carriedout, with the goal of achieving |de | < 10−29 –10−28 e cm. Besides performing the four-way chopthat adds to the eEDM signal, other chops that can serve as sanity checks include chopping thepolarization of the depletion laser for the first or second strobe-sequence and chopping the signof rotation ωrot → −ωrot. Unlike other eEDM experiments where the direction of electric field isapplied by a pair of parallel plates can be reversed, the direction of electric field cannot be chopped
in the same sense for the JILA eEDM experiment. The electric field direction is in effect always“inward” with respect to the circular motion. However, chopping for systematics from motional
magnetic fields arising from E~ ×~v can be easily performed by reversing the sign of rotation, whereas
for beam experiments, the same chop requires building a second source of molecules symmetrically
about the electric field plate setup. With Kevin Cossel and Matt Grau leading the charge on thecoherence time experiments, I am confident that the systematic evaluation will proceed speedily,and I look forward to a new limit on the eEDM coming forth from the ion trap setup!
In the longer term, we have plans to switch from HfF+ to ThF+ , a molecular ion that shares
many of the advantages offered by HfF+ , except that ThF+ is better: firstly, Eeff ≈ 90 GV/cm [55],170
which is three times higher than that of HfF+ , and secondly, the 3 ∆1 state is likely to either be
the true electronic ground state or no more than 315 cm−1 above the ground state [5]. In either of
those cases, the 3 ∆1 level is likely to be more long-lived than the present lifetime of the 3 ∆1 level in
HfF+ . Unfortunately, the issues with using ThF+ are the same as they were for HfF+ six years ago:
more spectroscopic information about ThF+ (as well as neutral ThF) needs to be obtained, fromwhich the quantum state preparation and state detection schemes have to be worked out. Dan
Gresh has revived the frequency-comb-enhanced velocity-modulation spectroscopy technique for
ThF+ in a discharge tube, with which he has started to observe some ThF+ transitions. Hopefully,
in the near future, sufficient ThF+ transitions can be identified and the discharge tube setup can beconverted into a second ion trap experiment for ThF+ state manipulation. With HfF+ and ThF+
experiments running in parallel, the JILA eEDM effort is an exciting one to watch, especially if anonzero eEDM is detected!
Returning to the coherent spectroscopy on trapped HfF+ molecular ions in a rotating bias
field, it is tempting to think about the rotating bias field technique in the context of the larger
molecular ion community. Many molecular ion experiments are built [89] either to carry out precision spectroscopy (e.g. on simple molecules like HD+ to test ab-initio theory [10] and to look
for time-variation in the mass ratios me /mp [77]) or to use the additional levels provided by therotational and vibrational degrees of freedom to perform quantum information processing [79].
With the exception of Penning trap experiments [85, 58], these molecular ion experiments tend tounder-utilize the electric dipole moment of molecular ions despite its importance as both a testof ab-initio calculations and as a degree of freedom in isolating particular Stark-Zeeman quantum
states for quantum information experiments. The application of a rotating bias field in a RF Paul
trap is a general technique that brings out the advantages of polar molecules while still preserving
the simplicity of an ion trap, and can have an impact on others in the molecular ion community
beyond those interested in an electron electric dipole moment search.

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