Small Diatomic Alkali Molecules at Ultracold Temperatures
A dissertation presented

byTout Taotao Wang
to
The Department of Physics
in partial fulfillment of the requirements
for the degree ofDoctor of Philosophy
in the subject ofPhysics
Harvard University
Cambridge, Massachusetts
October 2014c 2014 - Tout Taotao Wang
All rights reserved.

Dissertation Advisor: Wolfgang Ketterle

Author: Tout Taotao Wang

Small Diatomic Alkali Molecules at Ultracold Temperatures
Abstract
This dissertation describes experimental work done with two of the smallest diatomic alkali
molecules, 6 Li2 and 23 Na6 Li, each formed out of its constituent atoms at ultracold temperatures. The 23 Na6 Li molecule was formed for the first time at ultracold temperatures,
after previous attempts failed due to an incorrect assignment of Feshbach resonances in
the 6 Li+23 Na system. The experiment represents successful molecule formation around themost difficult Feshbach resonance ever used, and opens up the possibility of transferring
NaLi to its spin-triplet ground state, which has both magnetic and electric dipole moments
and is expected to be long-lived. For 6 Li2 , the experimental efforts in this thesis have
solved a long-standing puzzle of apparently long lifetimes of closed-channel fermion pairsaround a narrow Feshbach resonance, finding that the lifetime is in fact short, as expectedin the absence of Pauli suppression of collisions. Moreover, measurements of collisions of
Li2 with free Li atoms demonstrates a striking first example of collisions involving molecules
at ultracold temperatures described by physics beyond universal long-range van der Waals
interactions.

iii

Table of Contents

Abstractiii

Acknowledgements

ix

1 Introduction

1

2 Essentials of Diatomic Molecules3

2.1

Long-Range van der Waals Interactions . . . . . . . . . . . . . . . . . . . .

4

2.2

Full Molecular Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . .

8

2.3

Vibrations and Rotations . . . . . . . . . . . . . . . . . . . . . . . . . . . .

11

2.4

Angular Momentum Quantum Numbers Λ, Σ, and Ω . . . . . . . . . . . . .

13

2.5

Inversion Symmetries +/− and g/u . . . . . . . . . . . . . . . . . . . . . . .

16

2.6

Electric Dipole Moment . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

20

2.7

Electric Dipole Selection Rules . . . . . . . . . . . . . . . . . . . . . . . . .

23

2.8

Spin-Orbit Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

26

3 Feshbach Resonances and Molecule Formation

28

3.1

Scattering at Ultracold Temperatures. . . . . . . . . . . . . . . . . . . . .

29

3.2

The Radial Square Well Potential and Scattering Resonances . . . . . . . .

31

3.3

Feshbach Resonances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

35

3.4

The Asymptotic Bound-State Model . . . . . . . . . . . . . . . . . . . . . .

39

3.5

Molecule Formation around a Feshbach Resonance . . . . . . . . . . . . . .

42

3.6

The BEC-BCS Crossover . . . . . . . . . . . . . . . . . . . . . . . . . . . .

46iv

Table of Contents
4 Formation of 23 Na6 Li Molecules

48

4.1

Revised Assignment of Feshbach Resonances . . . . . . . . . . . . . . . . . .

48

4.2

Experimental Machinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

52

4.3

Molecule Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

53

4.4

Optimizing Decay Lifetime . . . . . . . . . . . . . . . . . . . . . . . . . . .

57

5 Molecules of 6 Li2 Around a Narrow Feshbach Resonance

59

5.1

A Long-Standing Puzzle in 6 Li . . . . . . . . . . . . . . . . . . . . . . . . .

59

5.2

Molecule Formation Around the 543 G Narrow Resonance . . . . . . . . . .

61

5.3

Collisions of 6 Li2 with Li and Na atoms . . . . . . . . . . . . . . . . . . . .

64

5.4

The Quantum Langevin Model for Collisional Loss . . . . . . . . . . . . . .

66

5.5

Quantum Depletion and Deviation from Universality . . . . . . . . . . . . .

69

6 Future Directions

71

6.1

A Long-Lived 23 Na6 Li Spin-Triplet Ground State . . . . . . . . . . . . . . .

71

6.2

Photoassociation Spectroscopy of 23 Na6 Li . . . . . . . . . . . . . . . . . . .

73

6.3

New Possibilities with Triplet Ground-State Molecules . . . . . . . . . . . .

79

A Asymptotic Bound State Model81

B Temperature and Density Measurements

88

C The Breit-Rabi Formula

91

References

96v

List of Figures

2.1

Van der Waals interactions between atom pairs . . . . . . . . . . . . . . . .

5

2.2

Two-atom energy levels coupled by the van der Waals interaction . . . . . .

7

2.3

The Lennard-Jones potential . . . . . . . . . . . . . . . . . . . . . . . . . .

9

2.4

Lowest ten electronic potentials of the NaLi molecule . . . . . . . . . . . . .

10

2.5

Vibrations and rotations of a diatomic molecule . . . . . . . . . . . . . . . .

12

2.6

Hund’s cases for electron angular momentum coupling to the molecular axis

14

2.7

Molecular potential curves for Li2 . . . . . . . . . . . . . . . . . . . . . . . .

19

2.8

Dipole-dipole interactions between a pair of heteronuclear molecules . . . .

21

3.1

Scattering from a spherically symmetric potential . . . . . . . . . . . . . . .

30

3.2

Scattering from a radial square well

. . . . . . . . . . . . . . . . . . . . . .

32

3.3

Resonant enhancement of scattering length in a radial square well . . . . .

33

3.4

Two-channel coupling model for a Feshbach resonance . . . . . . . . . . . .

35

3.5

Scattering length enhancement and bound-state behaviour . . . . . . . . . .

38

3.6

Open vs. closed-channel dominated Feshbach resonances . . . . . . . . . . .

39

3.7

Asymptotic bound-state model for Feshbach resonances . . . . . . . . . . .

41

3.8

Two-level Landau-Zener crossing . . . . . . . . . . . . . . . . . . . . . . . .

43

3.9

The BEC-BCS crossover in an ultracold gas of fermions . . . . . . . . . . .

47

4.1

Revised assignment of 6 Li+23 Na Feshbach resonances. . . . . . . . . . . .

50

4.2

Determination of Feshbach resonance location . . . . . . . . . . . . . . . . .

54

4.3

Experimental sequence for molecule formation . . . . . . . . . . . . . . . . .

55

vi

List of Figures
4.4

Absorption imaging of molecular clouds using dissociated Na and Li atoms

55

4.5

Separation of atoms and molecules in a magnetic field gradient . . . . . . .

56

4.6

Lifetime of trapped NaLi molecules . . . . . . . . . . . . . . . . . . . . . . .

58

5.1

Feshbach resonances in 6 Li2 . . . . . . . . . . . . . . . . . . . . . . . . . . .

60

5.2

Experimental sequence for 6 Li2 molecule formation . . . . . . . . . . . . . .

62

5.3

Absorption images of 6 Li2 molecules . . . . . . . . . . . . . . . . . . . . . .

63

5.4

Lifetime of a pure sample of 6 Li2 molecules . . . . . . . . . . . . . . . . . .

64

5.5

Lifetime of Li2 in the presence of free atoms . . . . . . . . . . . . . . . . . .

65

5.6

Quantum Langevin model for collisions involving ultracold molecules . . . .

67

5.7

Quantum depletion of vibrational decay in molecules . . . . . . . . . . . . .

70

6.1

Spin-triplet and singlet ground states of NaLi . . . . . . . . . . . . . . . . .

72

6.2

Stimulated Raman adiabatic passage for molecular state transfer . . . . . .

74

B.1 Temperature measurement of a 6 Li cloud . . . . . . . . . . . . . . . . . . .

89

vii

List of Tables

2.1

C6 coefficients and near-dissociation bound-state spacings . . . . . . . . . .

6

2.2

Key properties of various heteronuclear diatomic alkali molecules . . . . . .

23

3.1

Landau-Zener parameters from various molecule formation experiments . .

45

5.1

Two-body decay coefficients for Li2 with different collision partners . . . . .

67

viii

Acknowledgments

Someone once said, “There is no better place to spend your twenties than still in school.”
I can confirm that this has indeed been true of my graduate school years, and there aremany individuals to whom I am grateful for making things so. Foremost on the list is
Wolfgang Ketterle, whose infectious enthusiasm about science, gift for distilling complex
concepts down to simple explanations, and endless patience with his students make him arare breed of research mentor indeed. At times he prefaces the aforementioned explanations
by saying, “Let me explain this to you in a way you will never forget.” I expect that, having
had the privilege of doing research alongside Wolfgang, that there will be elements from thephysics of ultracold atoms that I will remember for the rest of my life. I will also cherish
the experience of pacing him for the first nine miles of a sub-eighty-minute half marathon,
before fading and finishing over a minute slower than his time.
It takes the endorsement of several faculty members to complete a dissertation, andI am grateful to my committee members John Doyle, Susanne Yelin and Markus Greiner
for serving in their respective capacities. John, in addition to being a leading expert on
everything having to do with cold molecules, was also my academic advisor, meaning thatmy progress through graduate school was directly related to his willingness to sign various
pieces of paper. Susanne is one of the most cheerful physicists I know, and moreover was
responsible for coordinating the grant that supported most of the work in this dissertation.
Markus, meanwhile, is someone who leaves you with a dozen different ideas for how to
upgrade your machinery each time you have an extended conversation with him. Research at
an institution of higher learning also cannot happen without the support of administrators,ix

Acknowledgments
and in my time at the Center for Ultracold Atoms I have received a great deal of assistancefrom Joanna Keseberg, David Fitzgerald, Paula Sack, and Jan Ragusa in areas ranging
from bizarre travel reimbursement requests to ordering something other than sandwiches forstudent lunch seminars. In addition, Lisa Cacciabaudo has been a source of encouragementin the last months of completing this dissertation, and typifies the department’s genuine
commitment to the well-being of its graduate students.
Although in principle I could have completed all of my research work alone, in practice it
was simply easier to have someone else shout: “Back,” “Keep going,” or “Next axis” acrossthe room while I adjusted the knobs on some mirror mount. In this regard, Myoung-Sun
Heo was a critical knob-tweaking partner for all of my most fruitful months of researchin graduate school. I will always be amazed at his capacity to do a full day of researchwork, go home to dinner with his wife and two beautiful daughters, and then return to
the laboratory again for more! Without his diligence and persevering attitude, the twomain scientific accomplishments of this dissertation would not have been possible. Timur
Rvachov has a healthy desire to challenge the status quo and ask hard questions, which
are valuable traits for a younger graduate student to have. Timur has become the resident
expert on our Cicero computer control system, and in addition led the charge to rebuild
a large part of our atom cooling hardware. I am happy to be leaving the laboratory inthe hands of a superior experimentalist. Dylan Cotta joined our team as the first Masters
student under my watch, and set a high bar for all such students to follow—most notably
providing a timely suggestion that we try to obtain our first molecule signal via a radiofrequency spin-flip to exclude free atoms from the image. Pascal Notz more than met thehigh standard that Dylan set, making impressive contributions during a difficult stretchof experiment repair. Colin Kennedy spent only a brief stint with us before trading thechallenge of making real molecules for the allure of generating artificial magnetic fields inthe next building over, but even in that short time, his eagerness and future potential wereapparent. I specifically acknowledge Timur, Colin, and Dylan for an unforgettable trip toa certain dancing establishment inn Anaheim during the 2012 DAMOP meeting.
xAcknowledgments
It took three full years before I absorbed enough knowledge from the more experienced
members of the team to take complete charge of the experimental work. In that time, I
learned from Gyu-boong Jo how to climb into awkward positions to do vacuum repairs,from Jae-Hoon Choi how to sufficiently tighten screws, from Ye-ryoung Lee how to give ourdiode lasers the magic touch, from Tony Kim how to build electronics to meet the sometimes
unusual needs of our laboratory, and from Caleb Christensen how growing up working in
the family hardware store is sometimes more important for doing research in experimental
physics than anything in the standard curriculum. To Caleb I owe a particular debt for his
heroic but ultimately unsuccessful first efforts towards molecule formation. Several younger
students have suffered through my Socratic method of explaining physics over the years. For
their perseverance, I thank Chenchen Luo, Derek Kita, Yijun Jiang, Li Jing and Gregory
Lau. Alan Jamison was persuaded enough by the promise of ultracold molecules to join
us as the new postdoctoral fellow. I wish him all the best for the coming months andyears. I have often joked that one can probably find every item in the Thorlabs catalogue
somewhere within the Center for Ultracold Atoms. In this and other ways, the collective
presence of the groups at Harvard and MIT is a real asset to atomic physics research, andI am grateful for the friends in the various groups who have given away optics or lent out
expensive equipment over the years.
Several chance encounters with senior researchers ended up leading to the breakthroughs
described in this dissertation. An extended discussion with Jook Walraven at the Les
Houches Summer School left me understanding the details of Feshbach resonances and how
to form molecules around extraordinarily narrow ones. Tobias Tiecke moved to Harvard
at just the right time for me to bombard him with questions about his Asymptotic Bound
State Model. Paul Julienne graciously sat down with me one day at lunch at a DAMOP
meeting and spent the next hour explaining to me a great deal about ultracold collisions.
Goulven Quéméner astonished all of us when we reached out to him about our observed
deviation from universality, by replying that he had already written a paper explaining
what we had found.
xiAcknowledgments
Having spent my undergraduate years at the University of Toronto, it was great to haveother alumni within the physics community at Harvard and MIT. Arghavan Safavi andMichael Yee, in particular, have been dear friends over the years. Joseph Thywissen at the
University of Toronto offered me the first chance to do experimental work in an ultracold
atoms laboratory. He has been a generous source of insight at DAMOP meetings in theyears since, including when he took a group of us out to dinner in Québec City. My path
towards a doctorate in physics started long before I entered university, and for giving me
the initial spark to pursue physics I thank Vida Ghaem-Maghami from Don Mills Collegiate
Institute.
In addition to publishing two journal papers during graduate school, I also had thechance to participate in the creation of two entertaining videos about my research work.
I am grateful to Tom Levenson and the team from the MIT Science Writing Program, as
well as Eric Ruleman and his team of expert filmmakers, for helping me tell the story ofthis dissertation on film.
Graduate school life is more than just turning knobs and aligning lasers, and Harvardin particular places an important emphasis on fostering a flourishing sense of community
among its graduate students. I spent two memorable years as a member of the Graduate
School of Arts and Sciences Resident Advisor team, and also relished being part of theDudley House community—everything from attending Senior Common Room dinners togetting a pair of top five finishes in the Charles River Run to score major points for Dudley during its Straus Cup-winning season of 2013-2014. The Harvard Graduate ChristianCommunity was an anchor for my life on campus for more than six years, and there I was
reminded that “worship and scholarship are not just two ships passing in the night.” In
Hope Fellowship Church, I found a home where the Gospel was preached with an authentic
sense of gladness, and where there existed a real, sacrificial commitment to serving thosein need. Training with Cambridge Running Club instilled in me a masochistic enjoymentof half-mile repeats. The mighty men of 21 Mellen kept me honest about all my bad habits
and were ideal companions for hiking adventures on both coasts.
xii

Acknowledgments
The most important part of graduate school is perhaps figuring out what to do afterwards. I thank Graeme Malcolm, John Nicholls, and Nils Hempler at M Squared Lasers forthe chance to join an impressive small company that is at the very cutting edge of photonics and quantum technologies. David Kemp, the Boston-based sales representative for M
Squared, facilitated the key introductions that resulted in me accepting a position that wasnever publicized, and that I never formally applied for. In the research world, people tend totreat sales representatives with everything ranging from apathy to contempt. Perhaps myexperience discovering an exciting opportunity at M Squared through Dave will highlightthe value of really engaging with people on the sales end of things.
My parents, Xiaoyong Tao and Chunying Wang, were the first investors in the enterpriseof my education, and without their insistence on the value of advanced schooling, I might
never have had the chance to consider doing doctoral work. While at Harvard I have also
been generously supported by a Postgraduate Scholarship from the Natural Sciences andEngineering Research Council of Canada.
I will end by noting that my biggest discovery during graduate school is not describedanywhere else in this dissertation. This discovery is not any fragment of scientific understanding, but a person. I am grateful for all the ways that Karlen Ruleman has become
part of my life.

xiii

Chapter 1
Introduction

The preparation and control of atoms at temperatures millions of times colder than that ofouter space has opened up numerous exciting scientific frontiers in the nearly two decades
since the dawn of Bose-Einstein condensation of alkali quantum gases. Ultracold atoms
trapped in optical lattices have been used to demonstrate textbook phase transitions aswell as to probe novel states of matter [Bloch et al., 2008]. Quantum-degenerate fermions
with strong interactions realized via Feshbach resonances have turned into high temperature
superfluids with transition temperatures that are sizeable fractions of the Fermi temperature[Ketterle and Zwierlein, 2008]. Synthetic gauge fields produced by off-resonant laser beams
have managed to coax neutral atoms into behaving like charged particles in a magnetic
field [Dalibard et al., 2011]. Rydberg atoms, whose valence electrons are nearly as far awayfrom their corresponding nuclei as possible, are becoming systems with unique potential
in quantum information [Saffman et al., 2010] and in many-body physics [Weimer et al.,2010]. Even exotic, many-valence-electron atoms like dysprosium [Lu et al., 2011] anderbium [Aikawa et al., 2012] have been cooled to quantum-degenerate temperatures.
However, matter in our universe does not exist solely in the form of dilute atomic
gases, but as more complex molecules. Thus, one active frontier in the growing field of
ultracold quantum matter is to extend the capabilities we have with atoms to the next
more complex object, diatomic molecules. The preparation of quantum-degenerate samples

1Chapter 1. Introductionof molecules will open up a range of new scientific directions [Krems et al., 2009], including
precision measurements, quantum computation, many-body physics with anisotropic longrange interactions, and ultracold chemistry. It is in this context that the experimental workin this dissertation has been done.
Specifically, I have worked with two of the smallest possible diatomic molecules built outof alkali atoms, 6 Li2 and 23 Na6 Li. For each molecule, the outcome of the experimental work
turned out to be very much related to it being composed of the smallest of alkali atoms. In
the case of 23 Na6 Li, Chapter 4 will describe how this molecule was finally successfully formed
around perhaps the most difficult Feshbach resonance ever used for molecule formation,
while Chapter 6 will try to anticipate the future scientific possibilities opened up by thecreation of this new molecule. For 6 Li2 , the experimental efforts described in Chapter 5
have solved a long-standing puzzle of apparently long lifetimes of closed-channel fermion
pairs around a narrow Feshbach resonance, and also demonstrated a striking first example
of collisions involving molecules at ultracold temperatures described by physics beyond
universal long-range van der Waals interactions. However, this dissertation will first startin Chapter 2 with introducing some of the concepts essential for understanding the physics
of diatomic molecules at ultracold tempeatures. This will be followed in Chapter 3 by an
in-depth treatment of Feshbach resonances between pairs of ultracold atoms, and how they
allow almost arbitrary tuning of the strength of inter-atomic interactions as well as theadiabatic conversion of free atom pairs into bound molecules in a specific internal quantum
state.

2

Chapter 2
Essentials of Diatomic Molecules

Molecular physics is a very old field, and our current body of knowledge about the physics
of diatomic molecules traces back to work done in the earliest days of quantum theory[Demtröder, 2005]. However, to experimentalists in the field of ultracold atoms, the appearance of near-quantum-degenerate molecules on the scientific landscape is something
recent [Ni et al., 2008]. Thus, many of the essential concepts needed for understanding ultracold molecules are still strange to younger researchers, and moreover, molecules are justsimply more complex and confusing objects to understand compared with atoms. They
have, in addition to electronic transitions, rotational and vibrational level structure. Moreover, these states are labelled by dizzying combinations of quantum numbers, and selection
rules for transitions between them become more elaborate.
Thankfully, one does not have to absorb all of molecular physics in order to have aworking knowledge for ultracold molecules. The goal of this chapter is to explain what theessential concept are, at a level that will be accessible to someone with a good grasp of
traditional atomic physics concepts like angular momentum coupling, perturbation theory,
two-level systems, etc. The chapter begins in Section 2.1 by discussing attractive vander Waals interactions between atom pairs. Section 2.2 introduces model potentials foratom pairs as well as realistic molecular potentials, and ends with the Born-Oppenheimer
approximation for solving the molecular Hamiltonian. The different electronic, vibrational

3

Chapter 2. Essentials of Diatomic Molecules
and rotational states in a molecule are covered in Section 2.3, and the following two sections,
2.4 and 2.5, explain all the different angular momentum and parity quantum numbers thatare important for identifying molecular states. Section 2.6 focuses on the useful property ofan electric dipole moment for diatomic molecules consisting of different atoms, and Section
2.7 returns to considering molecular states by deriving selection rules for possible electric
dipole transitions. The chapter ends with Section 2.8, which describes the effect of spin-orbit
coupling on molecules.

2.1

Long-Range van der Waals Interactions

Even in the limit of infinite separation, there are already attractive forces between atom
pairs that bring them together to form molecules. This is due to a simple theorem inquantum mechanics, which asserts that the van der Waals interaction between any two
ground-state atoms is always attractive. To see why the theorem is true, one can write
down the form of the dipole-dipole interaction energy between a pair of neutral atoms aand b (see for example [Griffiths, 1999], or [Jones et al., 2006])

Hdd =1 d~a · d~b − 3(d~a · R̂)(d~b · R̂)
4π0
R3

(2.1)

~ is thewhere 0 is the permittivity of free space, d~ = e~r is the dipole of each atom, and R
vector pointing from atom a to b (Fig. 2.1). In the semi-classical picture, neither atom a
nor b has a permanent electric dipole moment, but within each atom the orbiting electrons
produce a fluctuating dipole moment. The instantaneous dipole in one atom will induce asmall polarization in the partner atom, and the resulting interaction between fluctuating,induced dipoles is responsible for the van der Waals interaction.
In the quantum picture, if each atom is in its ground state |ga gb i, then the first order(1)

perturbation theory term for the interaction energy Eg= hga gb | Hdd |ga gb i=0 because of

the parity of d~a and d~b , which is the quantum way of saying that the atoms do not possess
permanent electric dipole moments. The leading order interaction term is then second-order4

Chapter 2. Essentials of Diatomic Molecules⃗⃗
atom batom aFigure 2.1: Van der Waals interactions between atom pairs arise from dipole-dipole coupling
between fluctuating dipoles in each atom. ~ra and ~rb are the electron position operators for~ is the vector going from one atom toeach atom centered on the corresponding nuclei. R
the otherin perturbation theory

Eg(2) =

X|ia ib i6=|ga gb i

| hia ib | Hdd |ga gb i |2
≡ −C6 /R6
E|ga gb i − E|ia ib i(2.2)

where |ia ib i are all the possible states of the two-atom system. Since the denominator
E|ga gb i − E|ia ib i is always negative if |ga gb i is the ground state, this implies that the leading
order interaction is of the van der Waals form −C6 /R6 . The expression for C6 given byP|hm|z|ni|2,
Eq. 2.1 and 2.2 resembles the single-atom static polarizability α = 2e2 m6=n (En −Em )
reflecting how the van der Waals interaction arises from induced dipoles.
In practice, a realistic calculation of C6 must be done numerically, accounting for notjust the valence electrons but also factoring in the core electrons, as well as valence-core
coupling. The latter two effects are small even in the heavier alkalis [Derevianko et al.,1999], and numerical results are usually accurate at the few percent level when compared
to experiments [Derevianko et al., 2001]. In addition to sources giving C6 for ground statealkalis [Derevianko et al., 1999, 2001; Mitroy and Bromley, 2003], there are references for theexcited states of heteronuclear alkali atom pairs [Bussery et al., 1987], as well for alkalineearth atoms [Mitroy and Bromley, 2003].

5

Chapter 2. Essentials of Diatomic Molecules
Atom Pair

C6 (a.u.)
1472
17314
4253
3058506 Li(2s)+23 Na(3s)
6 Li(2p)+23 Na(3s)40 K(4s)+87 Rb(5s)40 K(4s)+87 Rb(5p)Eb (2)-Eb (1) (GHz)
60
17
2.5
0.3

Table 2.1: Near-dissociation bound state energy spacings of different alkali atom pairs. The
left-most column specifies the electronic state of each atom in the pair. C6 coefficients are
obtained from [Mitroy and Bromley, 2003] for both atoms in their electronic ground states,
and from [Bussery et al., 1987] for the lowest energy state with one electronic excitation.
Spacings Eb (2)-Eb (1) are derived from the LeRoy-Bernstein formula, assuming a zero offset
ν0 .

The C6 coefficient determines the spacing of near-dissociation bound states of an atom
pair, up to an adjustable parameter that accounts for the deviation from van der Waals
behaviour at short-range. The relationship is parameterized by an analytical expression
known as the LeRoy-Bernstein formula [LeRoy and Bernstein, 1970] for the binding energy

Eb (ν) = (ν + ν0 )

h3

3

1/2

C6 µ3/2

Γ(7/6)
Γ(2/3)

3  3/2
2
π

(2.3)

where ν is an integer corresponding to the number of levels from dissociation, ν0 is theadjustable parameter, h is Planck’s constant, µ is the reduced mass of the two-atom system,and Γ is the Gamma function (a generalization of the factorial). From Eq. 2.3 it is clear thatthe binding energies grow rapidly with the cube of ν. Experimentally, one can determine
the C6 coefficient for an atom pair by measuring this characteristic fingerprint of near1/3

dissociation bound states and plotting Eb

vs. ν [Ni, 2009].

Table 2.1 compares the spacing between the first two bound states of NaLi vs. RbK,
assuming ν0 = 0 (potential almost deep enough to allow a new bound state at zero dissociation energy). Note that C6 is given in Table 2.1 in atomic units. To convert to S.I. units,
one should multiply by (1 Hartree) ×(a0 )6 = 9.57 × 10−80 J m6 , where a0 is the Bohr radiusand 1 Hartree = 4.36 × 10−19 J= 27.2 eV.
As a general rule of thumb, C6 gets larger for the heavier alkalis,1 because these atoms
1

See values tabulated in [Bussery et al., 1987], [Derevianko et al., 1999], [Derevianko et al., 2001], and6

Chapter 2. Essentials of Diatomic Molecules
E (cm-1)~32000E (cm-1)
2p+3p
4p+5p

~26000~17000~15000

2s+3p
2p+3s

Hdd

0

~13000~12800
0

2s+3s
Li+Na

4p+5s
4s+5p

Hdd

4s+5s
K+Rb

Figure 2.2: Two-atom energy levels coupled by the van der Waals interaction. The main
contribution to the van der Waals interaction in the na s+nb s ground state comes fromcoupling to na p+nb p. For na p+nb s, the dominant coupling is to na s+nb p, and vice versa.
are more polarizable. Their dipole matrix elements are larger, and the spacings between
electronic ground and excited states tend to be smaller. Fig. 2.2 shows an example comparison between Li+Na and K+Rb, where the van der Waals interaction in the na s+nb s
ground state comes primarily from coupling to na p+nb p. The d~a · d~b form of Hdd meansthat it does not couple na s+nb s to the lower lying states na p+nb s or na s+nb p. These states
are instead coupled only to one another by Hdd .
Compared to Li+Na, K+Rb has larger dipole matrix elements na(b) s da(b) na(b) p anda smaller na s+nb s to na p+nb p energy spacing, which accounts for the larger C6 coefficient
for atoms interacting in their electronic ground states. Moreover, since the dominant contribution to the van der Waals interaction in the electronically excited na p+nb s state comesfrom coupling to na s+na p, and vice versa, the corresponding C6 coefficients will be muchlarger, since this energy splitting is much smaller compared to the spacings between na s+nb s
and na p+nb p. For Li+Na the ratio of energy splittings is 15, while for K+Rb it is 130, which
qualitatively explains the magnitudes of their first-excited-state C6 coefficients compared tothose of the ground state. It is also apparent from Fig. 2.2 that na p+nb s and na s+nb p will
have van der Waals interactions of opposite sign. The lower-energy state will always havean attractive −C6 /R6 interaction, while for the higher-energy state the interaction will be[Mitroy and Bromley, 2003]

7

Chapter 2. Essentials of Diatomic Molecules
repulsive, because from Eq. 2.2, their energy-difference denominators have opposite signs.
Finally, it is important to note that the leading order long-range interaction may not be
the van der Waals term for electronically excited states. For homonuclear (identical) atom
pairs, like Li+Li or Na+Na, the leading term is in fact the first-order 1/R3 dipole term.
This is because electronic excitations for homonuclear pairs must be (anti)symmetrizedwith respect to exchange of the identical nuclei, so the proper wavefunction for a state with
one electronic excitation shared between two indistinguishable atoms is |Ψ± i = (|ga eb i ±√6 0, making the first non-zero term in the perturbation|ea gb i)/ 2. Now, hΨ| Hdd |Ψi =expansion of Hdd from Eq. 2.1 a −C3 /R3 dipole interaction. One consequence of this scalingis that the near-dissociation bound states of electronically excited homonuclear molecules
have much larger spatial extent compared to those of the electronic ground state.

2.2

Full Molecular Potentials

At shorter atomic separations R, the long-range 1/R6 van der Waals potential gives way
to more complex interactions. In particular, at short-range the overlapping electron cloudsof the two atoms produce a strong repulsive force. The Lennard-Jones potential (Fig. 2.3)
is one simplified way to qualitatively describe the full inter-atomic interaction. It takes theform
ULJ (R) =

C6
C12
− 6
12
R
R

(2.4)

where the repulsive term C12 /R12 is not physical, but is chosen for convenience of calculation[Israelachvili, 2011]. The location of the potential minimum is a simple expression Rmin =(2C12 /C6 )1/6 , and similarly the potential depth is Umin = −C62 /(4C1 2). For a molecularpotential of the Lennard-Jones form, a measurement of the near-dissociation energy levelspacing completely determines C6 , while knowing the offset of the first bound state fixes
C12 .

8

Chapter 2. Essentials of Diatomic Molecules

ULJ(R) = C12 / R12 – C6 / R6

Rmin = (2 C12 / C6)1/6

R

Umin = – C62 / 4 C12

Figure 2.3: The Lennard-Jones potential is one of the simplest qualitative ways of representing interatomic interactions.
Another simple analytical potential is the Morse potential
UM (R) = U0 (1 − e−a(R−R0 ) )2(2.5)

which has three parameters U0 , a and R0 instead of two in the case of the Lennard-Jones
potential. The energy level structure of the Morse potential is especially simple, with E(ν) =~ω0 (ν + 1/2) − ~2 ω 2 (ν + 1/2)2 /(4U0 ), where the effective harmonic oscillator frequencypω0 = a 2U0 /µ, and µ is the reduced mass [Demtröder, 2005]. However, the Morse potential
is also not physical, because in the limit R → ∞, UM (R) → U0 /e2aR and not −C6 /R6 .
Obviously, realistic potentials for molecules have many more adjustable parameters thaneither the Lennard-Jones or the Morse potentials. An example of realistic potentials for
NaLi are shown in Fig. 2.4. A single potential curve from such a plot can be described bymore than thirty different parameters [Steinke et al., 2012].
The ten potential curves in Fig. 2.4 all connect to one of three R → ∞ asymptotes,
corresponding to Li(2s)+Na(3s), Li(2p)+Na(3s) and Li(3s)+Na(3p), in order of increasingenergy. As explained in Section 2.1, potential curves asymptotic to the first two of theseseparated atom states scale as −1/R6 for R → ∞, while curves asymptotic to the thirdstate scale as 1/R6 . This difference between attractive and repulsive tails of the van der

9Chapter 2. Essentials of Diatomic Molecules

0.1
0.08
1

X Σ+
1
2 Σ+
1
3 Σ+
1
1Π
1
2Π
3
1 Σ+
3
2 Σ+
3
3 Σ+
3
1Π
3
2Π

U(R) (a.u.)

0.06
0.04
0.02
0
-0.02
-0.04

5

10

R (a.u.)15

20

Figure 2.4: Lowest ten electronic potentials of the 23 Na6 Li molecule. The axes are in atomic
units (a.u.) with R in units of a0 = 5.29 × 10−11 m and E in units of Hartrees. (Courtesyof Robin Côté and collaborators)

10Chapter 2. Essentials of Diatomic Molecules
Waals interaction is vanishing on the scale plotted in Fig. 2.4, and both can still result inbound states in the radial potential.
As the atoms approach one another, their original atomic orbitals s, p, d, etc. are nolonger the eigenstates of the total Hamiltonianp2j
P2~+ Σk k + V (~r, R)
H = Σj
2mj
2Mk

(2.6)

~ is the total
where the index j refers to the electrons, k refers to the nuclei, and V (~r, R)
Coulomb interaction potential that depends on the electron and nuclei positions, ~r = {~rj }~ = {R~ k } respectively, and is in general not separable. The Born-Oppenheimer approxand R
imation simplifies the solution to this Hamiltonian by assuming that, due to the more than
three-orders-of-magnitude difference in mass, electronic motion is much faster than nuclear
motion, meaning one can treat electronic motion with the nuclear coordinates essentially~
fixed. Thus, the Hamiltonian for electronic motion becomes Hel = Σj p2j /(2mj ) + V (~r, R),E~ and energies U (R),~ all of which are functions of thewith corresponding eigenstates ψel (R)~ = {R~ k }. The electronic eigenstates determine theinstantaneous positions of the nuclei R~ in which the nuclei move, and the Hamiltonian for nuclear motion becomes
potential U (R)~ The curves in Fig. 2.4 correspond to the different electronic
Hnuc = Σk Pk2 /(2Mk ) + U (R).
potentials U (R) for the nuclei, produced by electrons in the different states described by
the right-hand-side labels (e.g. X1 Σ+ ). These potentials only depend on the separation R
between nuclei, and the notation for their labelling will be explained in more detail later,in Sections 2.4 and 2.5.

2.3

Vibrations and Rotations

A diatomic molecule has three main degrees of freedom: electronic, vibrational, and rotational. The separations between electronic states form the largest energy scale in a molecule,with a typical order of magnitude of ∼10000 cm−1 . A given electronic potential includes aset of vibrational bound states (Fig. 2.5b), and these are the next largest energy scale in a11

Chapter 2. Essentials of Diatomic Molecules(a)(b) U(R)center ofmassR

rotationrotational levels

vibration

vibrational levels

Figure 2.5: Vibrations and rotations of a diatomic molecule. A given electronic potential
includes vibrational bound states with separations ranging from ∼1000 cm−1 to ∼0.1 cm−1
as one goes from the lowest to the highest states. A given vibrational bound state likewisecontains a ladder of rotational states, with typical spacings in the ∼0.01-0.1 cm−1 range forlow-lying vibrational states, and getting smaller for higher vibrational states.
molecule, ranging from ∼1000 cm−1 near the bottom of the potential to ∼0.1 cm−1 neardissociation [Demtröder, 2005]. Finally, a given vibrational bound state contains a ladder ofrotational states of the molecule. These have typical spacings in the ∼0.01-0.1 cm−1 range
for low-lying vibrational states, getting smaller for higher vibrational states. For reference,
0.1 cm−1 =30 GHz.
Since the typical energy scale of vibrational levels is much larger than that of rotational
levels, this means vibrational motion happens on much faster time-scales compared to thoseof rotational motion. Except in the extreme case of near-dissociation vibrational boundstates with large rotational excitation, a molecule will undergo many vibrational oscillationsin the time it takes to make one rotation (see Fig. 2.5a for illustrations of these motions).
Thus, we can first consider vibrational motion in the relative radial coordinate R in a given
electronic potential U (R) without including any rotational effects, and then simply add
rotation as a perturbation afterwards. For a perfectly harmonic potential, the vibrationalenergy levels would be quantized according to G(ν) = ~ωe (ν+1/2), where ωe is the harmonic
oscillation frequency of the electronic potential. In practice, electronic potentials such as
those in Fig. 2.4 are approximately harmonic only near their minima, and quickly become
anharmonic as one moves away. There is no analytic expression for the resulting energy

12Chapter 2. Essentials of Diatomic Molecules
spectrum, and vibrational energy levels for real electronic potentials are instead describedby a power series in ν +1/2 [Lefebvre-Brion and Field, 2004]. The spacings between adjacentlevels grow bigger with smaller reduced mass µ of the system, analogous the case of theharmonic oscillator, where ωe ∝ m−1/2 .
The inclusion of molecular rotations to this picture can be greatly simplified by assumingthat the molecule is a rigid rotor. Then the rotational energy becomes quantized according
to Hrot = J 2 /2I where J is the rotational angular momentum operator and I is the momentof inertia, which in the semiclassical picture is I = µR02 with R0 being the separation of theatoms. However, since in reality a molecule undergoes many vibrational oscillations during asingle rotation, R0 is in fact some weighted separation, such as the equilibrium internuclear
distance Re , that depends on the vibrational bound state in question [Lefebvre-Brion and
Field, 2004], and becomes larger as the vibrational quantum number ν increases. In thisframework, the rotational energy eigenvalues are

F (J) = Bν J(J + 1)

(2.7)

where Bν = ~2 /2I = ~2 /2µRν2 is the rotational constant that changes with the spatial extent
of the ν-th vibrational bound state. Note that Eq. 2.7 does not account for the additional
centrifugal distortions to the vibrational motion that comes with increasing rotation. A
more general expression is F (J) = Bν J(J + 1) + Dν (J(J + 1))2 , where Dν is the centrifugal
distortion term, and is typically a small correction on the order of 10−6 Bν [Lefebvre-Brionand Field, 2004]. The rotational eigenstates that define the molecular axis are simply
spherical harmonics YJM (θ, φ).

2.4

Angular Momentum Quantum Numbers Λ, Σ, and Ω

The electronic states of individual, separated atoms are given, in spectroscopic notation, as
2S+1 L . In the Born-Oppenheimer approximation from Section 2.2, when two such atoms
J

approach one another, the R → ∞ electronic states evolve adiabatically to connect to their
13

Chapter 2. Essentials of Diatomic MoleculesΩ =Λ+Σ
⃗
Λ

⃗

⃗

Ω

Σ

Figure 2.6: Hund’s cases for electron angular momentum coupling to the molecular axis.
(a) Quantum states are labelled by the projections of the electron orbital and spin angularmomentum on the molecular axis, Λ and Σ, along with their sum Ω. This is referred toas Hund’s coupling case (a), and is the main case that is valid for the molecules describedin this dissertation. (b) In this case, states are labelled by first adding the electron orbital~ + S,~ according to the rules of quantum mechanics, andand spin angular momenta, J~ = L
then specifying the projection on the molecular axis Ω = |mJ |. This is known as Hund’scase (c), and applies to very weakly bound molecules, as well as molecules to with large
constituent atoms and consequently strong spin-orbit coupling.
short-range counterparts. As shown in the labels on the right-hand-side of Fig. 2.4, theresulting electronic potentials U (R) are identified by the appropriate quantum numbers
at short-range 2S+1 ΛΩ . This expression is known as a term symbol, and is the molecularcounterpart of spectroscopic notation for atoms. The change in quantum numbers is dueto the fact that the Hamiltonian of the system (Eq. 2.6) is no longer spherically symmetric.
Ignoring rotations, there remains only one axis of symmetry along the line connecting
the two atoms, and electronic angular momenta must therefore be quantized along thismolecular axis (Fig. 2.6). The electronic wave function solutions to Eq. 2.6 for instantaneous~ thus become identified by their angular momentum projections along thisnuclei positions R
molecular axis, with different projections leading to different potentials U (R) for the muchslower vibrational motion of the nuclei.
The absolute value of the electronic orbital angular momentum along the molecularaxis is denoted Λ. As a historical artefact, Λ = 0, 1, and 2 are written as Σ, Π, and∆ respectively, and were chosen to be the Greek letter counterparts to atomic angularmomentum quantum numbers s, p, d, etc. The electronic ground state of separated atoms,
e. g. Li(2s)+Na(3s), produces only Σ molecular potentials, while Li(2p)+Na(3s) connects

14

Chapter 2. Essentials of Diatomic Molecules
to both Σ and Π potentials because the one unit of electronic orbital angular momentum
available in Li(2p) can have projection 0 or 1 along the molecular axis. In this case, Σ andΠ correspond to different potentials because they produce different electron distributions
around the molecular axis. Note, however, that there is no distinction made for negativevalues of Λ, because this corresponds in the semi-classical picture to an electron orbiting themolecular axis with opposite circulation, which does not change the energy of the system.
This means that each state Λ is doubly degenerate, and this degeneracy is only broken by
the rotation of the molecule in an effect called Λ-doubling.
The quantum number S corresponds to the sum of the two valence electron spins in a
diatomic alkali molecule, and takes on the values 0 or 1. The projection of S along themolecular axis is denoted by Σ (Fig. 2.6), which is confusing since the same symbol is also
used to represent Λ = 0 in the molecular term symbol. However, this notation conflict isinextricably part of the standard notation in molecular physics.
Different values of S lead to different potentials because of the effect of quantum statistics. In the S = 0 singlet state, the two-electron spatial wave function must be symmetric
under exchange, while in the S = 1 triplet states the wave function must be antisymmetric.
This implies that, compared to singlet electrons, triplet electrons are pushed out further
from one another and kept from overlapping. In a diatomic molecule, the attractive vander Waals potential is a result of electronic fluctuations polarizing the atoms and inducing
dipoles. As the atoms get closer, the polarization starts to create overlap between the valence electrons, but is suppressed by quantum statistics for electrons in the triplet state,thus reducing the attraction. Consequently, while at long range the van der Waals potential
is the same for the 1 Σ and 3 Σ ground states, at short range 3 Σ ends up being very shallow,
while 1 Σ is deep (see Fig. 2.4). In H2 , for example, the 3 Σ potential is so shallow thatno bound state exists. In NaLi, 3 Σ has a depth of 220 cm−1 while for 1 Σ the depth is7050 cm−1 [Mabrouk and Berriche, 2008].
For a fixed set of quantum numbers 2S+1 Λ, there is a manifold of potentials distinguishedby the prefixes shown in the right-hand-side labels of Fig. 2.4. For 1 Σ states, these prefixes
15Chapter 2. Essentials of Diatomic Molecules
are, in order of energy, X, 1, 2, ... and correspond to different separated atom electronic
states in the R → ∞ limit. For example, Li(2s)+Na(3s), Li(2p)+Na(3s), and Li(2s)+Na(3p)all have 1 Σ states, and these are written X1 Σ, 11 Σ and 21 Σ. For 3 Σ states the prefixes are
1 (or sometimes a), 2, 3, ... For all higher states (1 Π, 3 Π, etc.) the prefixes are simply 1,
2, 3, ... in order of ascending energy. In some cases, non-standard notation is used, e. g.
using purely letters or purely numbers, but whatever the symbols, the important point is
simply that they refer to the same angular momentum projections for different separated
atom asymptotes.
There is one final quantum number, Ω, that is often omitted from the standard notation
for identifying molecular potentials 2S+1 ΛΩ . It accounts for the relative alignment of orbitaland spin angular momentum projections Ω = mL + mS . This does not affect the electronic
distribution around the molecular axis, and thus does not alter the molecular potential.
The magnitude of Ω does become important when considering spin-orbit coupling between
states. Also, electronic potentials at large R are labelled by Ω alone, and not 2S+1 ΛΩ ,because there the dominant effect becomes the energy splitting from spin-orbit coupling inthe separated atoms, rather than differences in interaction energy arising from Λ or S.

2.5

Inversion Symmetries +/− and g/uAside from the quantum numbers specifying electronic angular momentum projections along
the molecular axis, there are two more quantum numbers +/− and g/u that label theelectronic potentials of a diatomic molecule. These correspond to two different kinds of
inversion symmetry: total inversion of all coordinates relative to an origin located at thecenter of mass of the molecule +/−, and inversion of only the coordinates of the nuclei g/u(this second symmetry exists only for homonuclear diatomic molecules, consisting of two
identical atoms).
All diatomic molecules possess the first of these symmetries, because an inversion of allcoordinates (electronic and nuclear) does not change the energy of the system, meaning

16Chapter 2. Essentials of Diatomic Moleculesthat the inversion (or parity) operator Π commutes with the Hamiltonian of the system.
Moreover, two inversion operations will restore the system to its original state Π(Π |ψi) =|ψi, meaning that eigenstates |ψi of the Hamiltonian (Eq. 2.6) can be classified as having+ or − parity with respect to total inversion.2
The action of Π on |ψi can be divided into three separate actions on the vibrational,
rotational, and electronic degrees of freedom of the molecule. Inversion leaves the vibrational wave function unchanged, since this depends only on the relative separation between
nuclei. Rotational wave functions take the form of spherical harmonics YJM (θ, φ), whichtransform under inversion according to Π YJM (θ, φ) = YJM (π − θ, φ + π) = (−1)J YJM (θ, φ).
Consequently, adjacent rotational levels J, J + 1 always have opposite parity.
The action of Π on the electronic part of the wave function is more complicated, since
the inversion occurs in the laboratory frame of reference while the electronic wave functions, in the Born-Oppenheimer approximation, are defined in a rotating molecular frameof reference. However, there is a surprising equivalence between an inversion in the laboratory frame of reference and a reflection in the x-z plane in the rotating molecular frame.3
Some authors thus refer to the +/− symmetry of the molecular state as simply reflection
symmetry, for example [Demtröder, 2005], leaving the reader confused about what this has
to do with parity, and how one chooses the seemingly arbitrary plane of reflection.
Using the equivalence of inversion in the laboratory frame and reflection in the molecular
frame, the electronic orbital angular momentum states |Λi transform under Π according to[Bernath, 2005; Brown and Carrington, 2003]

Π |Λi = (−1)Λ |−Λi

(2.8)

It is easy to check, in the limit of separate atoms, that the spherical harmonics for electronic
orbital angular momentum transform as such for a reflection in the x-z plane. For Λ > 0,2

For a detailed discussion of this subject, see [Bernath, 2005], [Demtröder, 2005], and [Brown and Carrington, 2003]
3
See Chapter 9.4 of [Bernath, 2005] and a nice derivation in terms of Euler angles in Chapter 6.9 of[Brown and Carrington, 2003]

17

Chapter 2. Essentials of Diatomic Molecules√
the properly (anti)symmetrized parity eigenstates are thus (|Λi ± |−Λi)/ 2. So the Πpotentials in Fig. 2.4 actually contain degenerate pairs of states with + and − parity,with the degeneracy ultimately broken by the different interactions of ±Λ with molecular√√rotation. Note that, for even Λ, (|Λi + |−Λi)/ 2 has + parity and (|Λi − |−Λi)/ 2 has −parity, but for odd Λ the opposite is true.
When Λ = 0, Eq. 2.8 reduces to Π |0i = |0i, which seems to imply that all Λ = 0
states have + parity. However, more accurately, Π |0i = 0̃ , because Π may turn one
Λ = 0 state into a different Λ = 0 state. As an example, consider |Λ = 0i = |p1 p−1 i,where in this notation we are considering, in the limit of separate atoms, one p-electronwith ml = 1 and another p-electron with ml = −1. Then Π |p1 p−1 i = (−1)(−1)−1 |p−1 p1 i,
because each individual valence electron state transforms under reflection in the x-z planein the same way as Eq. 2.8 prescribes for |Λi, namely Π |lm i = (−1)m |l−m i. The properly√
symmetrized parity eigenstates become |0± i = (|p1 p−1 i ± |p1 p−1 i)/ 2, meaning that a Σpotential connecting asymptotically to atoms each with a p-electron contains both + and− parity states. However, Σ potentials asymptotically connecting to s + s or s + p atoms
only have + parity states, and because of this ambiguity, the parity of Σ potentials must be
denoted explicitly as a superscript Σ± . This corresponds to the parity of the J = 0 rotational
states for all vibrational states in that potential, with higher J states alternating in parity.
Since this alternating parity forms a predictable pattern for increasing J, sometimes the
symbols e and f are used to denote the + or − parity of states when the (−1)J term isignored [Bernath, 2005].
The second inversion symmetry g/u exists only for homonuclear diatomic molecules, andcorresponds to an exchange of the nuclei. For identical nuclei, the system is indistinguishable
under this transformation, and thus eigenstates of homonuclear molecules can be labelled by
the terms g (gerade, for + symmetry of the wave function under the exchange of nuclei) andu (ungerade, − symmetry). An example of the lowest-lying potentials for the homonuclear
molecule Li2 is shown in Fig. 2.7, in which the g/u labels are added as suffixes to the term
symbol 2S+1 Λ±
g/u . While at first glance it seems like there are twice as many potential curves
18

Chapter 2. Essentials of Diatomic Molecules

Figure 2.7: Molecular potential curves for Li2 . For this homonuclear molecule, there isan additional symmetry g/u in the labels for the electronic potentials, corresponding to
exchange of identical nuclei. Plots taken from [Musial and Kucharski, 2014]

19

Chapter 2. Essentials of Diatomic Molecules
1 +as for the heteronuclear case, e. g. 21 Σ+
g and 1 Σu are both asymptotic to Li(2s)+Li(2p)while only 21 Σ+ is asymptotic to Na(2s)+Li(2p). The additional multiplicity produced by
the g/u label reflects the fact that in homonuclear molecules, there is built-in ambiguity
for whether the one unit of excitation comes from one atom or the other. From Section
2.1, in the limit of separate atoms, the properly (anti)symmetrized states with one unit of√electronic excitation are |Ψ± i = (|ga eb i ± |ea gb i)/ 2, with the + solution corresponding to
g-symmetry, and the − solution corresponding to u-symmetry.

2.6

Electric Dipole Moment

Heteronuclear diatomic molecules are those consisting of two different atoms. In thesemolecules, the electron is more likely to be near one atom than the other, resulting inan electric dipole moment along the molecular axis. However, in the absence of external
fields, the spherical harmonic rotational states of a molecule have no preferred direction,and thus there is no electric dipole moment in the laboratory frame. More concretely, if D
is the magnitude of the dipole moment along the molecular axis for a given vibrational andelectronic state, and r̂ is the unit vector pointing from the smaller atom to the bigger one,then the dipole moment of the molecule in the laboratory frame is d~ = D hψrot | r̂ |ψrot i = 0~ must be applied to
To induce an electric dipole moment, an external electric field E
break rotational symmetry. The electric field introduces off-diagonal terms of the form
~ is along the z-direction. This term couples, for example, the−E ẑ · Dr̂, assuming that E(J, mJ ) = (0, 0) and (1, 0) states, so that the resulting rotational Hamiltonian in the {|0, 0i,|1, 0i} basis becomes

0−EDẑ · r̂
Hrot = −EDẑ · r̂
2Bν

(2.9)

As E increases, it mixes the rotationally excited |1, 0i state into the ground state |0, 0i,
resulting in the dipole moment along the molecular axis becoming more and more alignedin the direction of the field. For E → ∞, the eigenstates of Hrot become |±i = (|0, 0i ±20Chapter 2. Essentials of Diatomic Molecules⃗⃗

Figure 2.8: Dipole-dipole interactions between a pair of heteronuclear molecules. The dipole
moment points from the smaller atom to the bigger one, meaning that the electron spends
more time near the smaller atom. This interaction is long-range and anisotropic.
√|1, 0i)/ 2, with |+i being the solution for an aligned dipole and |−i being that for ananti-aligned dipole. One can evaluate the magnitude of the aligned dipole moment to be√√√d~ = D h+| r̂ |+i = D/ 3 ≈ 0.58D, using ψ ± = (1± 3cosθ)/ 8π. This is not the full dipole~ will mix in other states besides |1, 0i. From
moment D because we have ignored how E
Eq. 2.9 we can define E0 ≡ 2Bν /D as the threshold field at which there will start to be asignificant admixture of the first rotationally excited state of the molecule, corresponding
simultaneously to the presence of a sizeable fraction of the full dipole moment. Note that forheteronuclear alkali molecules, the unit vector ~er for the dipole moment always points fromthe smaller atom to the bigger one. This is because the bigger atom is more polarizable,
meaning that its valence electron will be more easily pulled towards the smaller atom thanvice versa.
The possibility of having an aligned electric dipole moment is one of the most appealing
features of heteronuclear molecules, because, as illustrated in Fig. 2.8, it produces long-range
interactions between pairs of molecules of the same form as Eq. 2.1, except the resulting
interaction energy is first order in Ĥdip for aligned dipoles, and scales as 1/R3 . This dipoledipole interaction is also anisotropic, being repulsive for dipoles aligned side-by-side, andattractive for dipoles aligned end-to end.
Power law interactions of the form 1/Rn are called “long-range” if n ≤ 3. There are two

21

Chapter 2. Essentials of Diatomic Molecules
senses in which these interactions are long-range. The first is an energetic sense and thesecond is a collisional one. First, if one considers a dipole d~ interacting with a surrounding~ the resulting interaction energy of the one dipole canuniform density n of other dipoles d,
be written as
Z ∞ Z π Z 2π
U=
0

0

0

nd2 g(θ, φ) 2
R sinθ dφ dθ dR ∝4π0 Rn

Z

dR
Rn−2

(2.10)

with g(θ, φ) encapsulating the angular dependence of the dipole-dipole interaction. The
integral in R diverges for n ≤ 3, meaning that up to infinite range the surrounding dipoles
still contribute to the interaction energy term. Note that this argument is specific to dipolesinteracting in three dimensions. It is easy to see from Eq. 2.10 that dipole-dipole interactions
are short-range in the energetic sense in one and two dimensions, because the R-dependenceof the volume integral changes [Lahaye et al., 2009].
The second sense in which 1/Rn interactions are long-range for n ≤ 3 is in the context
of the two-particle scattering wave function. At zero temperature, two-body scatteringfrom short-range n > 3 interactions reduce only to the s-wave term in the partial wave
expansion, and can be replaced by zero-range delta function contact interactions. Forn ≤ 3 interactions, this is no longer valid. All partial waves still contribute to the scatteringwave function down to T = 0, and the potential cannot be replaced by a zero-range one[Lahaye et al., 2009]. This means, for example, that dipolar gases of identical fermions will
still collide and thermalize in the T → 0 limit.
The magnitudes of predicted dipole moments for the possible heteronuclear diatomic
molecules formed out of alkali atoms range from 0.47 Debye on the low end for NaLi to 5.5
Debye on the high end for LiCs (1 Debye = 0.4 ea0 where e is the elementary charge anda0 is the Bohr radius). Table 2.2 gives the dipole moments D for a representative set ofheteronuclear molecules that are currently being studied experimentally4 , along with their
4

Values for D are obtained from [Aymar and Dulieu, 2005] and references therein, except for that ofKRb, which is obtained from [Ni et al., 2008]

22

Chapter 2. Essentials of Diatomic Molecules

D (Debye)B0 (cm−1 )E0 (kV/cm)

23 Na6 Li

40 K87 Rb

87 Rb133 Cs

23 Na40 K

6 Li40 K

7 Li133 Cs

0.47
0.43
110

0.57
0.037
8

1.2
0.016
1.6

2.7
0.0097
0.44

3.5
0.30
11

5.5
0.22
4.9

Table 2.2: Key properties of a representative set of possible heteronuclear diatomic alkali
molecules, given in order of increasing dipole moment along the molecular axis D. The
rotational constant B0 of the absolute ground state (vibrational and electronic) is also
given, as is the threshold field E0 = 2B0 /D for inducing a significant fraction of the full
dipole moment of the molecule. Note that the breakdown field in air is 10 kV/cm

ground-state rotational constants B0 and threshold fields E0 required to align the dipoles.5
This is by no means an exhaustive list of all the possible heteronuclear combinations thatcan be formed out of the alkalis Li, Na, K, Rb, Cs, and Fr.
For two aligned, side-by-side dipoles, Eq. 2.1 gives an expression for the interactionenergy Udd = d2 /(4π0 R3 ). Assuming that the dipoles are R = 532 nm apart in a 1064nm optical lattice, Udd /h = 300 Hz for NaLi and 28 KHz for LiCs. The two orders ofmagnitude difference between the two is accounted for by the d2 scaling of Udd . Still, bothare still far larger than the magnetic dipole-dipole interaction energy between atoms. Evenfor dysprosium, which has a magnetic moment µ = 10µB and is the most magnetic atom,
Udd /h = µ0 µ2 /(4πR3 )= 10 Hz, where µ0 is the permeability of free space, µB is the Bohrmagneton, and we have again used R = 532 nm.

2.7Electric Dipole Selection Rules

The quantum numbers from Sections 2.4 and 2.5 allow us to define selection rules forthe allowed vibrational, rotational and electronic transitions in diatomic molecules. The
simplest selection rules have to do with the inversion symmetries of the molecule from
Section 2.5. The electric dipole operator d~ has − symmetry under both a total inversion of
all coordinates Π, and under exchange of identical nuclei in a homonuclear molecule. Thus,
5

Values for B0 obtained from using Re from [Aymar and Dulieu, 2005] and taking B0 = ~2 /2µRe2 , which
for KRb is well within 1% of the experimental value from [Ni, 2009], and in general should be accurate towell within 10%23

Chapter 2. Essentials of Diatomic Molecules
allowed electric dipole transitions must connect states of opposite symmetry, + ↔ − andg ↔ u. Transitions between states of the same symmetry are electric-dipole forbidden.
In order to consider further selection rules, we can write the dipole operator moreP
~ 1 + Z2 eR~ 2 , where ~ri and R~ j represent the electronic andconcretely as d~ = −e ~ri + Z1 eR
nuclear coordinates respectively, and their origin is located at the center of mass of themolecule. We can write this as d~ = d~el + d~nuc , and the question of allowed transitions
becomes a question of initial and final states |ψi i and |ψf i for which the matrix elementhψf | d~ |ψi i =6 0.
In the Born-Oppenheimer approximation, |ψi can be separated into electronic and nuclear components |ψi = |ψel i |ψnuc i ≡ φχ, and following [Demtröder, 2005], we can write
Z Z~
φ∗f χ∗f (d~el + d~nuc )φi χi d3~r d3 R

Z
Z
3
∗~
∗
~
φf del φi d ~r χi d3 R
= χf
Z

Z
3
∗
∗~
~
+ χ dnucφ φi d ~r χi d3 R

hψf | d~ |ψi i =ff(2.11)

This conveniently separates hψf | d~ |ψi i into two contributions. For transitions within theRR~ = 0 due to the parity of d~el , while forsame electronic potential, χ∗f
φ∗f d~el φi d3~r χi d3 R
RR
~ = 0 because oftransitions between different electronic states, χ∗f d~nucφ∗f φi d3~r χi d3 R
the orthonormality of φi and φf .
In the first case of transitions within the same electronic potentialhψf | d~ |ψi i =Z~χ∗f d~nuc χ∗i d3 R

(2.12)

from which we can immediately see that if the molecule is homonuclear, then d~nuc = 0, implying that there are no allowed ro-vibrational transitions. For heteronuclear molecules, rovibrational transitions are allowed. If we separate χ into rotational and vibrational parts χ =R
ξ(R)YJM (θ, φ), the angular part of the integral in Eq. 2.12 becomes YJ∗0 M 0 d~nuc YJM dΩ.
The selection rules for such an integral are familiar from the Wigner-Eckart Theorem as

24

Chapter 2. Essentials of Diatomic Molecules
applied to alkali atoms [Steck, 2010], and the result is ∆J = ±1 and ∆MJ = 0, ±1. Historically, ∆J = 1 transitions have been referred to as belonging to the R-branch, while∆J = −1 belongs to the P-branch. The ∆J = 0 case is allowed by the Wigner-Eckart theorem, but is forbidden by parity. If the electronic potential were perfectly harmonic, then
only ∆ν = ±1 vibrational transitions would be allowed, but since real electronic potentials
for molecules are highly anharmonic, no selection rules exist for ν.
For transitions between different electronic potentials, Eq. 2.11 becomeshψf | d~ |ψi i =
=

Z

Z

χ∗f

Z

~ el (R)χi d3 R~
χ∗f D

φ∗f d~el φi d3~r~
χi d3 R
(2.13)

The angular part of this integral gives us the same constraints ∆J = 0, ±1, and these are all
allowed as long as the parity selection rules + ↔ − and g ↔ u are followed. To give someexamples, still only ∆J = ±1 are allowed for 1 Σ+ →1 Σ+ transitions, while only ∆J = 0 isallowed for 1 Σ+ →1 Σ− . Finally, ∆J = 0, ±1 are all allowed for 1 Σ+ →1 Π.
~ el (R) aroundWe can go one step beyond this and do a Taylor series expansion of D
~ el (R0 ) [Demtröder, 2005; Bernath, 2005].
some R = R0 and keep only the leading term D~ el (R0 ) hνf |νi i, with D~ el (R0 )Then, ignoring rotations, Eq. 2.13 becomes hψf | d~ |ψi i = D
representing the dipole matrix element for the electronic transition at some mean R = R0 ,and with an additional vibrational wave function overlap term hνf |νi i. This last term issome times referred to as the Franck-Condon factor of the transition, and is a qualitative
way of estimating the magnitude of the matrix elements between different vibrational levels.
For larger ν, the weight of the wave function becomes concentrated at the classical turning
points of the potential, and having a large Franck-Condon overlap factor becomes equivalent
to having the classical turning points of νi and νf line up. In the semi-classical picture,
an electronic excitation happens on a time scale much faster than vibrational motion ina molecule, meaning that the nuclei will essentially have the same positions and velocities
before and after the excitation.

25

Chapter 2. Essentials of Diatomic Molecules

2.8

Spin-Orbit CouplingThus far, we have treated the electronic, rotational and vibrational states of diatomic
molecules in an idealized, Born-Oppenheimer approximation context. However, there exist
various additional terms that modify molecular states in significant ways. One of these is
the spin-orbit coupling term [Demtröder, 2005; Lefebvre-Brion and Field, 2004]

Hso =

X

ai~li · ~si

ai~li =

i

2
ef f
X
α2 Z
k

k=1

2
2 rik

~lik

(2.14)

where ~li and ~si are the individual electron orbital and spin angular momenta, α = 1/137 is
the fine-structure constant, rik is the distance from the i-th electron to the k-th nucleus, ~likis the corresponding orbital angular momentum, and Zkef f is the effective nuclear charge.
Spin-orbit coupling is responsible for splitting 2S+1 ΛΩ states depending on Ω, which captures
the relative alignment between the electronic orbital momentum projection Λ and the spin
projection Σ.
The spin-orbit coupling term Hso also couples states from different electronic potentials
according to + ↔ −, g ↔ u, ∆Ω = 0, ∆S = 0 or ±1, ∆Λ = ∆Σ = 0 or ∆Λ = −∆Σ = ±1.
For example, among the lowest lying electronic potentials of Li+Na in Fig. 2.4, 21 Σ+ and13 Π are coupled by Hso . If a bound state in 21 Σ+ and another in 13 Π fall are separated byless than the scale of the spin-orbit coupling energy ai ~2 , they will be mixed by Hso and theresulting eigenstate will possess both singlet and triplet wave function components. Thisis significant because electric dipole transitions do not change the spin of the molecule, so
connecting singlet states to triplet states and vice versa requires spin-orbit coupling of thesenear-degenerate levels.
The spin-orbit coupling energy scale can be estimated by simply taking it to be the spinorbit splitting in the corresponding atom [Brown and Carrington, 2003]. For instance, inFig. 2.4, 21 Σ+ and 13 Π both connect to the Li(2p)+Na(3s) asymptote, so we can estimate
the spin-orbit coupling between these two potentials from the fine-structure splitting of26

Chapter 2. Essentials of Diatomic Molecules
6 Li(2p), which is 10 GHz or 0.3 cm−1 and ranks as the smallest among the alkali atoms.

This means that, given the uncertainty of the best available theoretical potentials, it isextremely challenging to predict where there will be two near-degenerate states that mix
via spin-orbit coupling. At present, all efforts to search for such a coupled state as an avenue
for transferring singlet molecules to triplet, and vice versa, have been unsuccessful [Steinke
et al., 2012].

27

Chapter 3
Feshbach Resonances and Molecule Formation

The process of two atoms joining together to form a molecule is one of the simplest reactions in chemistry. Under normal conditions, this happens when collisions arising from therandom thermal motion of the atoms brings two of them together in just the right way toform a molecule. With ultracold atoms, this random thermal motion is almost completelygone, and atom pairs can be adiabatically converted to a bound-state via something calleda Feshbach resonance. The rest of this chapter will explain how this works.
In Section 3.1, we start by reviewing the highlights of the theory of low-energy scattering. This is followed by a treatment of resonant scattering in a simple, square-well model
potential in Section 3.2, which introduces many of the concepts involved with Feshbachresonances. Section 3.3 discusses, in the context of two coupled square wells, how Feshbachresonances arise when a bound-state in one molecular potential is tuned to coincide withthe zero-energy asymptote of a colliding atom pair. This is followed by an description of theasymptotic bound-state method in Section 3.4, which is a simple yet realistic way of modeling how Feshbach resonances occur. The topic of molecule formation around a Feshbachresonance is treated in detail in Section 3.5, and the chapter concludes with the theory of
the BEC-BCS crossover for ultracold fermionic atoms around a Feshbach resonance.

28

Chapter 3. Feshbach Resonances and Molecule Formation

3.1

Scattering at Ultracold Temperatures

From the basic theory of scattering in quantum mechanics [Landau and Lifshitz, 1977],
when two atoms undergo an elastic collision, their wave function, far away from the rangeof the spherically symmetric interaction potential U (r), must be a sum of free particle plane
wave and spherical wave solutions in the relative coordinate ~rψk (r, θ) ∼ eikz + f (θ)

eikr
r

r→∞

(3.1)

where k is the free atom wave vector, r is the separation in the relative coordinate system,and θ is the angle from the initial collision axis. The function f (θ) is called the scattering
amplitude (Fig. 3.1). The general solution can be written in the partial wave expansion asψk (r, θ) =∞X

al Pl (cos θ)Rkl (r)

(3.2)

l=0

where Pl (cos θ) are the Legendre polynomials and Rkl (r) satisfies the radial equation
1 d
r2 dr


 

l(l + 1) 2µ
2 dRkl2r+ k −− 2 U (r) Rkl = 0
dr
r2
~

(3.3)

where µ is the reduced mass of the two-atom system. The l = 0 term is referred to ass-wave, the l = 1 term as p-wave, etc.
The r → ∞ form of the solution to Eq. 3.3 is1π
Rkl ∼ sin(kr − l + ηl )
r
2

(3.4)

If the scattering potential U (r) = 0, then the phase shifts ηl = 0 as well, and substituting
the solution in Eq. 3.4 back into Eq. 3.2 along with the coefficientsal =1(2l + 1)il eiηl
2k

29

(3.5)

Chapter 3. Feshbach Resonances and Molecule Formation

r

θ

U(r)

r

Figure 3.1: Two atom scattering in relative coordinates from a spherically symmetric potential U (r). Far away from the range of the potential, as r → ∞ and U (r) → 0, the wave
function in the relative coordinate ~r is a sum of free particle plane wave and spherical wave
solutions.
recovers the partial wave expansion for eikz . Thus, the effect of U (r) at short range is seenin the r → ∞ limit only as phase shifts ηl to the radial wave function.
Combining Eq. 3.4 and 3.5, the scattering amplitude becomesf (θ) =∞
X

(2l + 1)fl Pl (cos θ)

(3.6)

l=0

fl =

1 2iηl(e− 1)2ik= k −1 eiηl sin ηl=1
kcot ηl − ik

= k −1 (sin ηl cos ηl + i sin2 ηl )which includes several useful and equivalent ways of writing the contribution fl from eachpartial wave to f (θ).
The total scattering cross section is then
∞

σ=

4π X
(2l + 1) sin2 ηl
k2

(3.7)

l=0

In the zero temperature limit k → 0, tan ηl → k 2l+1 , or more accurately, tan ηl →30

Chapter 3. Feshbach Resonances and Molecule Formation(kal )2l+1 [Walraven, 2010] where al is the scattering length for the l-th partial wave, which
will be defined concretely in Section 3.2. To avoid a conflict in notation, the l = 0 scattering
length is written simply as a to avoid confusion with the Bohr radius a0 . Thus, at ultracold
temperatures, all other partial wave contributions aside from l = 0 can be neglected. The
limiting temperature can be estimated by requiring kal  1 for l ≥ 1, which gives T 
Tlim ∼ 1 mK for alkali atoms, with Tlim varying somewhat for different atoms according toTlim ∼ µ−2 a−1
l . A good estimate for al is ∼ 50 − 100a0 , although in rare cases, a term al
might diverge for l > 0 due to the presence of a higher-partial-wave scattering resonance, inwhich case its contribution to f (θ) and σ can no longer be neglected. The topic of scatteringresonances will be treated in greater detail throughout the rest of this chapter.
When the two colliding atoms are identical bosons (or fermions), the scattering wave
function must be (anti)-symmetrized with respect to exchange of the atom pair. This iscarried out in the scattering amplitude f (θ) → f (θ) ± f (π − θ), where the + term corresponds to symmetrization for bosons, and the − term corresponds to anti-symmetrization
for fermions. For l = 0, f (θ) is independent of θ, which means that for fermions the antisymmetrized scattering amplitude is zero. In other words, at ultracold temperatures, s-wave
scattering of fermionic atoms is prohibited by quantum statistics.

3.2

The Radial Square Well Potential and Scattering Resonances

The simple example of two atoms scattering from a spherically symmetric square well interaction potential (Fig. 3.2) already captures the key concepts in the theory of Feshbachresonances: phase shifts, resonant enhancement of the scattering cross section, equivalence
to a delta function pseudo-potential, presence of a near-dissociation bound state, etc. At ultracold temperatures, where only the s-wave term is important, the scattering problem canbe solved in two separate regions, r < r0 and r > r0 , followed by connecting the solutions
at r = 0 in a way that satisfies continuity conditions.

31

Chapter 3. Feshbach Resonances and Molecule Formation

(a)

U(r)

(b)

U(r)
g δ(r)

r0
r

r

-U0

Figure 3.2: Scattering from a radial square well with depth U0 and range r0 . In the zerotemperature limit, the square well in (a) and the delta potential in (b) give the same s-wave
phase shift η0 at large distances for g = 4π~2 a/µ, where a is the s-wave scattering length
The radial Schrödinger equation (Eq. 3.3) can be solved by substituting χ0 (r) = rRk0−~2 d2
χ0 (r) + U (r)χ0 (r) = Eχ0 (r)2µ dr2(3.8)

The separate, un-normalized solutions inside and outside the potential well U (r) are thenχ0 (r) =A sin(K+ r)

r < r0χ0 (r) =B sin(kr + η0 )r > r0(3.9)

where the solution for r < r0 is constrained by the boundary condition χ0 (0) = 0, while
the r > r0 solution has η0 as a free parameter. We have defined the wave vectors K+ , κ0 ,2 = k 2 + κ2 , U = ~2 κ2 /(2µ), and E = ~2 k 2 /(2µ) → 0 in the limit of zeroand k, with K+000

temperature.
To connect the solutions in Eq. 3.9 at r = r0 , we require χ0 (r) and dχ0 (r)/dr to becontinuous. Combining these two requirements gives

K+ cot(K+ r0 ) = k cot(kr + η0 )(3.10)In the k → 0 limit this becomes κ0 cot(κ0 r0 ) = 1/(r + η0 /k), which assumes that η0  1.
The s-wave scattering length can be defined in these limits as a = −η0 /k, or for arbitrary

32

Chapter 3. Feshbach Resonances and Molecule Formation

(a)

(b)
χ0(r)

a

(cos η0) k(r – a)

r
r0
π/2

3π/2

5π/2

κ0r0

Figure 3.3: Resonant enhancement of scattering length a in a radial square well potential.
(a) The scattering length a diverges for discrete values of κ0 r0 . (b) At ultracold temperatures, kr0  1, meaning that on the scale of the potential well U (r) the solution for r > r0
is linear χ0 (r) ∼ (cos η0 )k(r − a), while the solution for r < r0 oscillates rapidly
η0 as a = 1 − tan (kr0 + η0 )/(kr0 ), resulting intan(κ0 r0 )a = r0 1 −κ0 r0(3.11)

This implies that for discrete well depths corresponding to κ0 r0 = (2n − 1)π/2, n = 1, 2, 3...
the scattering length a diverges (Fig. 3.3a). Moreover, since for typical potentials κ0 r0  1,away from these divergences, the value of a quickly returns to the background scattering
length value abg = r0 , which makes sense since a is a measure of the size of the scattering
potential.
The solution in Eq. 3.11 for the scattering length completely determines the scattering
amplitude and the total scattering cross section of the potential via Eq. 3.6 and 3.7, withthe latter of these being σ = 4πa2 for ka  1 and σ = 4π/k 2 for ka  1. The limitka  1 is called the unitarity limit, because sin2 η0 = 1 in Eq. 3.7. Also, as illustrated
in Fig. 3.2b, the square well with depth U0 produces the same phase shift η0 as a delta
function potential with height g = 4π~2 a/µ, which means they have the same scattering
properties. The potential U (r) = gδ(r) is called the s-wave pseudo-potential counterpart
to the square well potential. Thus, when a diverges, the square well potential acts like a
zero-range contact interaction with diverging interaction strength g.

33

Chapter 3. Feshbach Resonances and Molecule Formation
Finally, the scattering length a also affects the relative amplitudes of the solutions forr < r0 and r > r0 . This is shown in Fig. 3.3b. For r > r0 , the k → 0 oscillating solution
is linear on the scale of U (r), and a first-order Taylor series expansion at r = r0+ givesχ0 (r) ∼ (cos η0 )k(r − a). Thus, one can equivalently define the scattering length a as ther-axis intercept of the tangent to χ0 (r) at r = r0 . Note that the slope of the tangent is
proportional to cos η0 . For small a, cos η0 ∼ 1. Since both χ0 (r) and dχ0 (r)/dr are required
to be continuous at r = r0 , it means that the slow oscillations of the wave function for r > r0
will have much higher amplitude than the fast oscillations within the range of the potential
well r < r0 (as depicted in Fig. 3.3b). However, whenever a diverges, cos η0 =0, and the two
oscillation amplitudes will be exactly equal. Thus, in the case of diverging a, the scatteringwave function within the potential well reaches its maximum amplitude.
The condition κ0 r0 = (2n − 1)π/2 for diverging a corresponds to the appearance of a
new bound state in the square well potential U(r) at the E = 0 dissociation threshold.
To see this, we can solve the radial Schrödinger equation (Eq. 3.3) for negative energies
Eb = −~2 κ2 /(2m).

χ0 (r) =A sin(K− r)

r < r0χ0 (r) =B e−κr

r > r0(3.12)

2 = −κ2 + κ2 . Imposing the continuity conditions again for χ (r)where we have defined K−00

and dχ0 (r)/dr gives
K− cot(K− r0 ) = −κ(3.13)In the k → 0 limit, κ = −κ0 cot(κ0 r0 ). From Eq. 3.11, κ = 1/(a − r0 ), which for diverging
scattering length a  r0 means the energy of the near-dissociation bound state is Eb =−~2 /(2µa2 ). In addition, the wave function of the bound state outside the range of thepotential well falls off as e−r/(a−r0 ) , meaning that for diverging a, the near-dissociation
bound state has a very large spatial extent a that stretches far beyond its classical turning
point. This two-particle bound state with infinitesimal binding energy and large spatial
34

Chapter 3. Feshbach Resonances and Molecule Formation

closed channel

U(r)
(a)

U(r)
(b)
ε

ε

r0

-UC

r

-UO
electronspin
nuclearspin

open channelrU(r) =

|O>
−

|C>

−
0 0
0 ∞

r < r0r ≥ r0Figure 3.4: Two-channel coupling model for a Feshbach resonance. (a) For an atom pairscattering along the open-channel interaction potential (red), a scattering resonance occurs
when a closed-channel potential for the same atom pair with different internal states (blue)
has a bound state resonant ( = 0) with the zero-energy asymptote of the open channel. The
atom pairs are both in their na s+nb s electronic ground states, and differ only in their internal
electronic and nuclear spin states. The total spin projection mF of the open-channel atom
pair is the same as that of the closed-channel atom pair. (b) A simplified model consistingof an open-channel scattering potential (red), a single bound-state of interest in a closed
channel potential (blue), and a coupling term U1 between the two channels
extent is called a long-range (or halo) dimer.

3.3

Feshbach Resonances

In Section 3.2, scattering resonances in a radial square well potential occurred for discrete
well depths at which a new bound state emerged at the dissociation threshold. Yet interaction potentials between real atoms (as described in Section 2.2) do not in general
have variable depths. However, a pair of atoms scattering along some interaction potential
can experience something analogous called a Feshbach resonance. The model for how thishappens is shown in Fig. 3.4a.
The interaction potential along which the atom pair in question scatters is called theopen-channel. On its own, this open-channel potential has some existing background scattering length abg , based on the phase shift it imposes on the scattering wave function. If
we consider another nearby interaction potential that dissociates into individual atoms in
35

Chapter 3. Feshbach Resonances and Molecule Formationdifferent internal states, then a Feshbach resonance can occur whenever one of the boundstate in this second, closed-channel potential coincides with the zero-energy asymptote of
the open-channel ( = 0 in Fig. 3.4a). When this happens, the scattering length of the
open-channel potential diverges, exactly as if its depth had been adjusted to allow a new
bound state to appear at the dissociation threshold.
The detuning  between the closed-channel bound state and the open-channel zero~ The open andenergy asymptote can be tuned by applying an external magnetic field B.
closed-channel potentials dissociate into atom pairs with different internal states, so theyexperience a differential Zeeman shift with applied magnetic field, resulting in = 0 + ∆µB(3.14)

where 0 is the energy offset at zero field, while ∆µ is the differential magnetic moment
along the field direction between open and closed-channel atom pairs. From Section 2.1 weknow that the near-dissociation bound-state spacings for molecular potentials is ∼GHz forthe first two states, and rapidly grows for the more deeply bound ones. This is comparable
to the hyperfine spacings in alkali atoms [Steck, 2010], which determine the separations
between open and closed-channel asymptotes in Fig. 3.4a. Since ∆µ for atom pairs withdifferent electronic spins is on the order of the Bohr magneton µB = 1.4 MHz/G, thismeans that with typical laboratory magnetic fields of up to ∼ 1000 G,  can be tuned by atmost 1 − 2 GHz. Consequently, for most alkali atom pairs such as Li+Na and Li+Li, theonly experimentally accessible Feshbach resonances are those produced by the least-boundvibrational state of a closed-channel potential.
The exactly solvable radial square well model for resonant scattering from Section 3.2
can be extended to two coupled square wells (Fig. 3.4b) in a manner that still captures theessential physics of Feshbach resonances [Chin, 2005]. In this simplified two-channel model,
the open-channel potential is the same as that of the radial square well from Section 3.2,
with a non-resonant U0 such that the scattering length of the open channel alone is abg ≈ r0 .

36

Chapter 3. Feshbach Resonances and Molecule Formation
The closed-channel potential is modelled as an infinite square well with the same radius r0
and with a single, near-resonant bound state of interest at an energy offset . Within therange of the two potential wells r < r0 , there is a term U1 that couples the open and closed
channels. This term is critical, because without it, scattering in the open channel will be
unaffected by the closed-channel bound state.
In the presence of coupling U1 , there is a Feshbach resonance when the closed-channelbound state approaches the zero-energy asymptote of the open channel, which causes thescattering length a to diverge (Fig. 3.5a) according to




∆µ∆B
∆B
a = abg 1 −= abg 1 −
 − res
B − Bres(3.15)

where ∆B ∼ U12 (abg − r0 )2 /abg parametrizes the width of scattering length enhancement[Chin, 2005]. The U1 -dependence of ∆B comes from the fact that increasing U1 increases
the mixing between open and closed-channels near resonance, resulting in a larger range
over which the closed-channel bound state enhances scattering in the open channel. The
abg dependence comes from the discussion in Section 3.2 of how a larger abg results ina higher amplitude of the open-channel scattering wave function within the range of thesquare well r < r0 , which again results in a stronger coupling between channels, because
the coupling depends on both U1 and the radial wave function overlap between open andclosed channels. A bound state also appears together with scattering length enhancementfor  < res (Fig. 3.5b), and behaves near res exactly like the long-range dimer from Section
3.2, with energy
−~2
−~2
=
E=
2µa2
2µa2bg

B − Bres∆B

2(3.16)

and wave function ψ ∼ e−r/(a−r0 ) in the classically forbidden region r > r0 .
Note, however, that the value  = res at which a diverges and the near-dissociation
bound state appears is not  = 0, exactly where the closed-channel bound state crosses the
open-channel zero-energy asymptote. Instead, the center of the Feshbach resonance res isshifted by ∆µ∆B from  = 0. This is because, in the presence of the coupling term Ω,37

Chapter 3. Feshbach Resonances and Molecule Formation(a)a–ħ2/(2μa2)

(b)
E

|O>

Δμ ΔB
|C>

abg

Δμ ΔB
εres

ε=0

εres

ε

Figure 3.5: Scattering length enhancement and bound-state behaviour in the two coupledsquare wells model of a Feshbach resonance. (a) Near the resonance res , a diverges fromthe background value abg , with a width of scattering length enhancement parametrized by∆B. (b) The behaviour of the bound state energy (blue) is analogous to that of a longrange dimer, and arises due to an avoided crossing between the open-channel |Oi and closed
channel |Ci
the closed-channel bound state |Ci and the open-channel scattering state |Oi behave likea two-level system with an avoided crossing (Fig. 3.5b). For   res , the bound-stateenergy becomes asymptotic to the energy of the energy of |Ci, meaning that, far away fromresonance, the bound-state is entirely in the closed-channel. However, near resonance, thebound-state of the two coupled channels is actually a superposition of the open-channel
scattering scattering wave function and the closed-channel bound state. Its energy thus
becomes quadratic near res according to Eq. 3.16, and only reaches the E = 0 dissociation
limit at res = ∆µ∆B.
In the limit  = 0 , the bound-state wave function is actually entirely in the open channel,
which makes sense given that the slope of the bound-state energy there is zero. To estimate
the range around the avoided crossing over which the closed-channel wave function enters
into the superposition, we can calculate the point at which the near-dissociation bound-stateenergy in Eq. 3.16 has the slope ∆µ of the true closed channel bound state with changing
B. We can write this as−~2 d
2µa2bg dB

B − Bres
∆B

2
= ∆µ

(3.17)
2~
which gives B − Bres = −ζ∆B or  − res = −ζ∆µ∆B, where ζ = ∆B∆µ/ µa
2 is theparameter describing the fraction of ∆B over which the bound-state is open-channel dom38

Chapter 3. Feshbach Resonances and Molecule Formation

(a)

(b)

a

a

ζ << 1abg

ζ >> 1
abg

E

E

|O>
|C>

|O>
|C>

Δμ ΔB
ε=0

εres

Δμ ΔB
ε=0

ε

εres

ε

Figure 3.6: Open vs. closed-channel dominated Feshbach resonances. (a) A closed-channeldominated resonance has ζ  1. The top plot (red) shows the scattering length modificationnear resonance, while the bottom plot (blue) shows the bound-state energy. The shaded
region  − res  ζ∆µ∆B, where the bound-state energy closely follows that of the openchannel, is much smaller than the range of scattering length enhancement ∆µ∆B. In thisregion, the bound-state has a vanishing closed-channel admixture. (b) In an open-channeldominated resonance, ζ  1, and the shaded region essentially spans the entire range ofscattering length modification2~
inated (Fig. 3.6). If we define an energy scale E0 = (∆B∆µ)2 / µa
2 , then the open-channel-

dominated region is equivalently  − res  E0 . This is also called the single-channel
approximation region because here, both the scattering and the bound-state solutions behave exactly as if the single open-channel potential on its own had been adjusted to allow
a new bound-state to appear near dissociation, without any closed-channel potential being
involved. Feshbach resonances with ζ  1 are called open-channel dominated, while thosewith ζ  1 are called closed-channel dominated.

3.4

The Asymptotic Bound-State Model

Even though interaction potentials between real atoms (such as those described in Section2.2) are much more complicated than the two coupled square wells model from Section 3.3,
the question of how Feshbach resonances occur for a given atom pair can still be simplified to39

Chapter 3. Feshbach Resonances and Molecule Formation
be one that depends on the same three parameters from before: the background scattering
length abg of the open-channel scattering potential, the initial, zero-field energy offset 0of the closed-channel bound-state responsible for causing the Feshbach resonance, and thecoupling matrix element U1 between the open and closed channels. These are the ingredientsof the asymptotic bound-state model, which is a simple yet accurate way of describing the
Feshbach resonances of a particular atom pair.1
For accurate predictions of Feshbach resonance locations, the only required ingredient is
the free parameter 0 . Then, using the Breit-Rabi formula for the interaction fo atoms withan external magnetic field [Steck, 2010], we can immediately predict the magnetic fields at
which the closed-channel bound-state will intersect the open-channel asymptote (Fig. 3.7).
Here we are assuming that the magnetic field B has a vanishing perturbation on the shapeof molecular potentials describing interacting atom pairs, and only shifts their asymptotes
in energy. This is a good assumption because Zeeman-shift energy scales are much smaller
than those of molecular potentials.
The main difference between the toy model in Fig. 3.7a and the realistic model inFig. 3.7b is a more elaborate treatment of the closed-channel bound-states that are responsible for producing Feshbach resonances. Taking into account hyperfine structure and shiftswith magnetic field, the full interaction Hamiltonian for an atom pair in their electronic
ground states can be written as

H =V (r) + Hhf + Hz

(3.18)

1
V (r) = [Vs (r) + 3Vt (r)] + [Vt (r) − Vs (r)] ~sa · ~sb
4
Hhf =Ahf,a ~ia · ~sa + Ahf,b ~ib · ~sb~~ − γN,a ~ia · B~ − γN,b ~ib · B
Hz =γe (~sa + ~sb ) · B(3.19)

where the complex form of V(r) reduces to the triplet potential Vt (r) for any triplet state,1This model is explained in great detail in [Tiecke et al., 2010], [Tiecke, 2009], and [Walraven, 2010], withthe latter two sources being more pedagogical in nature

40Chapter 3. Feshbach Resonances and Molecule Formation

(a)

(b)
E

E

ε0

B

B

Figure 3.7: Asymptotic bound-state model for Feshbach resonances. The locations of Feshbach resonances for an atom pair can be predicted with only the zero-field energy 0 of theclosed-channel bound-state as a free parameter. (a) In this toy model, two spin-down atoms
mS = −1 in the open-channel (red) can be coupled to another spin-triplet closed-channelbound-state with some zero-field energy offset 0 (blue). The mS = 1 and mS = 0 spin
projections of the closed-channel intersect with the open-channel at magnetic field values
B that can be predicted with the Breit-Rabi formula for the interaction of atoms with an
external magnetic field. (b) A realistic model includes all the hyperfine states within themolecular vibrational level that have the correct quantum numbers to couple to the openchannel. These hyperfine states are also split by couplings to one another. In this model,
a measurement of the location of the lowest field resonance immediately fixes 0 , and thus
the locations of all the other resonances
and to the singlet potential Vs (r) for any singlet state. The asymptotic bound-state model
considers only the least bound states of Vt (r) and Vs (r) rather than the full potentials. The
atomic hyperfine constants are written as Ahf,a/b , while γe and γN,a/b are the electronic andnuclear gyromagnetic ratios respectively.
The hyperfine coupling term Hhf is the coupling term connecting open and closed channels. It connects the open-channel scattering state to any closed-channel bound-state thathas the same total spin-projection mF = mS + mi,a + mi,b [Walraven, 2010]. Thus, within
the same least-bound vibrational state in the spin-triplet potential, there are many hyperfine states that can produce Feshbach resonances in the open channel. The energies of these
hyperfine states with increasing magnetic field B is described by the usual interplay between
Hhf and Hz . States from within the spin-singlet potential can also have the same overall
projection mF as the open-channel and be responsible for producing Feshbach resonances.
These spin-singlet hyperfine states do not shift in energy with magnetic field B, except at
places where they intersect spin-triplet bound states. There, the same coupling term Hhf
produces avoided crossings between singlet and triplet states, perturbing both in ways must41

Chapter 3. Feshbach Resonances and Molecule Formation
be accounted for in quantitative predictions of Feshbach resonance locations. Appendix A
includes a concrete example of how one takes into account the energy shifts and couplings
for all the hyperfine states responsible for producing Feshbach resonances for an atomic
pair, and make quantitatively accurate predictions of Feshbach resonance locations.
In addition to predicting the locations of Feshbach resonances, the asymptotic boundstate method can also describe resonance widths. These depend on the coupling matrix
element U1 between open and closed channels. The part of U1 that depends on the electronic
states of the atom pair is fixed by Eq. 3.18. To obtain the radial wave function overlap, theasymptotic bound-state model assumes that the overlap has negligible contribution fromthe short-range part of the closed-channel wave function. Thus, we can replace the detailed√

2

closed-channel wave function with that of a halo dimer e−2µ b r/~ , where b is the closedchannel binding energy (to be distinguished from 0 . The overlap with the open-channel isthen one that depends on the amplitude of the open-channel scattering wave function nearr = 0, which, as discussed in Section 3.2, depends on abg . Thus, the strongest Feshbachresonances are the ones with large scattering length already in the open-channel alone.

3.5

Molecule Formation around a Feshbach ResonanceAround a Feshbach resonance, the combination of an adjustable detuning  and a coupling
matrix element U1 between the closed-channel bound-state and the open-channel scattering
state means that a separated atom pair in the open-channel can be adiabatically converted
into a bound molecular state in the closed-channel in a manner analogous to a Landau-Zenercrossing. In a two-level Landau-Zener problem, two states, |1i and |2i, are coupled by amatrix element U1 = ~Ω, resulting in the Hamiltonian H given in Fig. 3.8. As the detuning
 between the two states is adiabatically varied across the resonance at  = 0, the systemfollows the dressed eigenstates of H, converting the |1i state to |2i, and vice versa. The
region in  over which the dressed states contain a significant admixture of both basis states
has width ∼ ~Ω, and the condition for adiabaticity is that  is varied over this region in a42

Chapter 3. Feshbach Resonances and Molecule Formation

|2>

E

|1>
− /2
H=
ħΩ

|1>
ħΩ
|2>

|1>
ε

|2>
ħΩ
/2

ħΩ
ε=0

Figure 3.8: In a two-level Landau-Zener crossing, the states |1i and |2i are coupled by Ω.
If the detuning  is adiabatically varied across the  = 0 resonance, the system follows the
dressed eigenstates (blue), converting |1i to |2i, and vice-versa
time much longer than 1/Ω, with Ω being referred to as the Rabi frequency. Quantitatively,
the probability of conversion is [Steck, 2010]
P = 1 − exp−π ~Ω2
2 |d/dt|= 1 − exp (−2πδLZ )(3.20)

where δLZ = ~(Ω/2)2 / |d/dt| is called the Landau-Zener parameter, and d/dt is adiabaticfor δLZ  1
In the case of a Feshbach resonance, the analogous avoided crossing is between the openchannel separated atom pair and the closed-channel bound-state (as explained in Section
3.3). Thus, when the magnetic field B is adiabatically varied across the resonance, atom
pairs are converted into closed-channel bound molecules. The main distinction is that fora Feshbach resonance, the open-channel consists of a continuum of scattering states. Thismeans that, while in the two-level Landau-Zener problem, there is an equal admixture
on resonance of the two uncoupled states, for a Feshbach resonance the corresponding
eigenstates are entirely open-channel on resonance.
In order to determine what the value of |dB/dt| required for adiabaticity, we needto know the analogous Landau-Zener parameter δLZ . The Laudau-Zener problem for an
atom pair near a Feshbach resonance has been solved exactly for homonuclear pairs at zero43Chapter 3. Feshbach Resonances and Molecule Formation
temperature [Köhler et al., 2006]. For a pair of atoms in a box of volume VδLZ =1 2π~ abg ∆B
V µ dB/dt(3.21)

where µ is the reduced mass of the pair and the 1/V factor comes from the normalizationof free-particle plane-wave solutions [Chwedeńczuk et al., 2004; Cumby et al., 2013]. Thisis then generalized to a uniform density of atoms n Köhler et al. [2006]

δLZ = n2π~ abg ∆Bµ dB/dt(3.22)

where n = N/V is the density, and represents the fact that each atom now has N equally
likely pairing partners.
For heteronuclear atom pairs at finite temperature, the situation is complicated by
reduced phase-space overlap between the different atomic species. At higher temperatures,an atom is less likely to find a partner close enough in phase space to form a molecule [Hodby
et al., 2005]. Moreover, for a heteronuclear atom pair, the different trapping frequencies
of different atoms further reduces phase space overlap [Deuretzbacher et al., 2008], as does
spatial separation in a Bose-Fermi mixture below the condensation temperature TBEC forthe bosonic component [Cumby et al., 2013]. However, if we still naively apply Eq. 3.22 toa heteronuclear atom pair and just take n to be the larger of the two component densities,
we obtain a generous upper bound on δLZ for a particular magnetic field sweep dB/dt. In
practice, experimental magnetic field sweeps to form molecules fall in the range δLZ ∼ 0.1
to 1, as shown in Table 3.1,2 meaning that the prediction in Eq. 3.22 is useful for providing
an initial target dB/dt for successful molecule formation.
2

Entries for ∆B and abg obtained from [Chin et al., 2010], except those for 6 Li40 K, which are obtained
from [Wille et al., 2008]. Experimental parameters obtained from [Xu et al., 2003] for Na2 ; [Greiner et al.,2003] for K2 ; [Hodby et al., 2005], [Dürr et al., 2004], and [Syassen et al., 2006] for Rb2 ; [Herbig et al., 2003]
for Cs2 ; [Papp and Wieman, 2006] for 85 Rb87 Rb; [Spiegelhalder et al., 2010] for LiK; and [Zirbel, 2008] forKRb

44

Chapter 3. Feshbach Resonances and Molecule Formation
Resonance
907 G 23 Na2
202 G 40 K2
155 G 85 Rb21007 G 87 Rb2
20 G 133 Cs2
265 G 85 Rb87 Rb
372 G 85 Rb87 Rb
168 G 6 Li40 K
546 G 40 K87 Rb

∆B
(G)
1
8
11
0.2
0.005
1
6
0.08
3

abg
(a0 )
63
174
440
100
160
213
213
60
189

nexp
( cm−3 )1.7 × 1014
1.4 × 1013
1011
5 × 1014
1013
7 × 1012
7 × 1012
2 × 1012
8 × 1012

dB/dt(G/ms)
100
25
10
10
0.05
2.2
14
0.23
7

E0
(kHz)
180
3.3 × 104
1.5 × 10637
0.0038
2.1 × 103
7.7 × 104
0.13
1.3 × 104

EF
(kHz)
6.6
3.8
1.8
1.8
1.1
1.8
1.8
15
2.8

Ω
(kHz)
14
33
50
3.5
0.25
9.6
24
4.2
21

exp
δLZ

0.39
1.6
0.05
0.97
0.1
0.66
0.63
0.34
1

Table 3.1: Generalized Landau-Zener parameters from various molecule formation experiments. The entries under ∆B, abg , nexp , and dB/dt are obtained from the sources given
exp
are calculated based on the outlinedin the text. The entries under E0 , EF , Ω, and δLZtheory. For heteronuclear atom pairs, nexp is taken to be the smaller of the two component
densities.

The expression in Eq. 3.22 can be rewritten as a combination of energy scales

δLZ =where Ω =

1
~

q

3/2

~Ω2
d/dt

(3.23)

1/2

ẼF E0 /3π is the Rabi frequency for atom-molecule coupling, E0 is as

given in Section 3.3, and ẼF = (6π 2 n)3/2 ~2 /µ is the effective Fermi energy, which expresses
the atomic density n in energy units for bosons as well as for fermions.
There are a number of additional techniques of forming molecules around a Feshbachresonance that are not directly relevant to the experiments described later in this dissertation. Two of these are radio-frequency association [Zirbel et al., 2008b], and modulation of
the magnetic field at a frequency resonant with the molecular binding energy [Thompson
et al., 2005]. Both require the target molecular bound-state to be open-channel-dominated.
Photoassociation is a third technique for forming molecules out of ultracold atoms [Joneset al., 2006]. I will describe this technique in greater detail in Section 6.2 in the context of
future efforts deriving from the work in this dissertation. For now, it is sufficient to mention
that the efficiency of photoassociation depends on the overlap of the open-channel scatter-

45

Chapter 3. Feshbach Resonances and Molecule Formation
ing wave function and a short-range electronically excited bound-state wave function. As
discussed in Section 3.2, this overlap can be enhanced near a scattering resonance.

3.6

The BEC-BCS Crossover

The first signature of Feshbach resonances in ultracold atoms was dramatically enhanced
inelastic collision rates in bosonic 23 Na, leading to strong loss at specific magnetic fields[Inouye et al., 1998]. This is because, where the two-body scattering length a is enhanced,
three-body inelastic collision rates are enhanced even more [D’Incao and Esry, 2005], leading
to rapid loss of the ultracold atom sample near a Feshbach resonance. This loss happens
via a process called three-body recombination, in which a collision involving three atoms
leaves two of them in a bound state, and the binding energy is released as kinetic energy of
the collision products.
Thus, it was only with the arrival of ultracold fermionic atoms that Feshbach resonances
became more than just a way of tuning three-body loss [Ketterle and Zwierlein, 2008]. A pairof fermions in different internal states can collide via s-wave scattering. Near a Feshbachresonance, where the scattering length a diverges, the fermion pairs exist in a BCS-likepaired state on the a < 0 side, where the effective pseudo-potential interaction (given in
Section 3.2) is strongly attractive, and as a Bose-Einstein condensate of bound halo dimers
on the a > 0 side (Fig. 3.9). The entire region near resonance is then called the BEC-BCS
crossover.
Three-body recombination is suppressed in such a system, because it would require acollision between at least two fermions in the same internal state. In the limit of zerotemperature, this is forbidden by the quantum statistics, and in general the process is
suppressed by (kRe )γ , where Re is characteristic spatial extent of the product bound-state
in decay by three-body recombination, and γ is some numerical factor greater than one[Petrov et al., 2004]. Since typical de-Broglie wavelengths are ∼ 1 µm for ultracold atoms
while Re ∼ 50a0 , this means (kRe )γ is vanishingly small for ultracold fermions. In the case46

Chapter 3. Feshbach Resonances and Molecule Formation

crossovera

E
B
BEC ofhalo dimers

BCS pairing

Figure 3.9: The BEC-BCS crossover in an ultracold gas of fermions. A gas consisting of
ultracold fermions in two different internal states exists near a Feshbach resonance as a
BCS-like paired state on the a < 0 side, and as a Bose-Einstein condensate of bound halo
dimers on the a > 0 side. Decay via three-body recombination is suppressed by quantum
statistics even in the presence of diverging a.
of halo dimers on the a > 0 side of the Feshbach resonace, their formation is not suppressedby quantum statistics because of their large spatial extent as a diverges. However, decay ofthese pairs to more deeply bound states by an inelastic collision with another pair or a free
atom is still suppressed by the same mechanism as above.
Consequently, in ultracold Fermi gases, Feshbach resonances become a knob that allows
interparticle interactions to be tuned to arbitrary values. This has resulted in the demonstration of high-temperature superfluidity of BCS-paired fermions (at a significant fractionof the Fermi temperature TF ) as well as Bose-Einstein condensation of weakly bound halo
dimer molecules [Ketterle and Zwierlein, 2008].

47

Chapter 4
Formation of 23Na6Li Molecules

In this chapter I will describe one of the two main scientific contributions of this dissertation,
the successful formation of 23 Na6 Li molecules around a Feshbach resonance at 745 G after
extensive previous efforts proved to be unsuccessful [Christensen, 2011]. In Section 4.1, I
will explain how the previous unsuccessful attempts at molecule formation were due to anincorrect assignment of the Feshbach resonances in the 6 Li+23 Na system. This is followed bya brief description in Section 4.2, of the apparatus used for molecule formation experiments.
The procedure for successful molecule formation is explained in Section 4.3, and the chapter
concludes in Section 4.4 with a discussion of the lifetime of NaLi molecules against collisional
decay. The work described in this chapter has been published in [Heo et al., 2012].

4.1

Revised Assignment of Feshbach Resonances

Feshbach resonances in the 6 Li+23 Na system were the first ever observed between atoms oftwo different species [Stan et al., 2004]. A characteristic fingerprint of three closely spaced
resonances was obtained for magnetic fields of 746 G, 760 G and 796 G, for Li in |ms mi i =|−1/2 1i and Na in |−1/2 3/2i. These were assigned to be resonances produced by theleast-bound vibrational state of the spin-triplet potential with spin projection mS = 1.
As described in Appendix A, there are precisely three molecular hyperfine states with theright quantum numbers to couple to the open-channel atoms, and by choosing the triplet
48

Chapter 4. Formation of 23 Na6 Li Moleculesand singlet binding energies to be E1 = 5710 MHz and E0 = 4245 MHz respectively, thelocations of the resonances can be reproduced by the asymptotic bound-state model from
Section 3.4. This assignment was confirmed by a full coupled-channels calculation [Gacesa
et al., 2008], which assigned a background scattering length of abg = 14a0 and ∆B = 0.04 G,
0.3 G and 2 G for each of the resonances, or E0 /h = 3 Hz, 180 Hz and 8 kHz if we use theenergy scale E0 from Section 3.3 characterizing the width of the open-channel-dominatedregion around resonance.
An earlier effort to produce NaLi molecules using this assignment of Feshbach resonances
was unsuccessful despite an exhaustive search across all experimentally feasible resonancelocations and for a wide range of magnetic field sweep rates [Christensen, 2011]. The reason
for this turned out to be an incorrect assignment of Feshbach resonances by [Stan et al.,2004] and [Gacesa et al., 2008]. As illustrated in Fig. 4.1, the revised assignment foundthat the previously observed Feshbach resonances below 800 G were in fact produced byweak dipole-dipole coupling of the unpaired electron spins in the colliding atoms [Schuster
et al., 2012]. This dipole-dipole coupling has an angular dependence (Section 2.6) thatallows mixing of partial waves, such that the s-wave open-channel wave function can couple
to d-wave, or J = 2 closed-channel molecular bound states with two units of rotational
angular momentum. Under the revised assignment, there is a far greater multiplicity ofstates with hyperfine and rotational projection quantum numbers to couple to the openchannel. In particular, there are eleven states in total with mS = 1 that intersect in energy
with the open-channel near 800 G, and it is sheer coincidence that only three of them can bereadily observed experimentally, producing the deceptive fingerprint of resonance locations
that mimicked the case of typical hyperfine-induced Feshbach resonances. It was only byidentifying the locations of resonances at higher magnetic fields B that a strong discrepancy
emerged [Christensen, 2011; Schuster et al., 2012], confirming that the revised assignment
does indeed more correctly describe the Feshbach resonances in the system.
Note that there are still Feshbach resonances produced by s-wave, J = 0 closed-channelbound states via the more typical mechanism of hyperfine coupling. However, these states
49

Chapter 4. Formation of 23 Na6 Li Molecules

(b)

(a)

Figure 4.1: Revised assignment of 6 Li+23 Na Feshbach resonances. (a) In the original assignment, the three observed resonances were assigned to the mS = 1 projection of theleast-bound vibrational state of the spin-triplet potential, with three hyperfine states having the right quantum numbers to couple to the open-channel (circled). The variation of
the open-channel energy with magnetic field B is shown as a black dashed curve, while thebound-state energies are in blue. (b) In the revised assignment, resonances below 1000 G
are produced by weak dipole-dipole coupling, which couples the s-wave scattering in the
open-channel to d-wave, or J = 2 closed-channel molecular bound states with two unitsof rotational angular momentum. Compared to the typical hyperfine coupling, this results
in a much larger multiplicity of states with the right hyperfine and rotational quantum
numbers (red) to couple to the open channel (black, dashed). The closed-channel boundstates corresponding to the typical, hyperfine coupled Feshbach resonances are still present(blue), but these are much more deeply bound than previously assumed. The plot in (b)was taken from [Schuster et al., 2012]

50

Chapter 4. Formation of 23 Na6 Li Molecules
are much more deeply bound than previously thought, and thus produce resonances atmagnetic fields B > 1000 G that are at the edge of what our experimental apparatus (Section
4.2) can access. The binding energies for the triplet and singlet states, as derived from therevised resonance assignments, are E1 = 9353 MHz and E0 = 9384 MHz respectively[Schuster et al., 2012]. From Table 2.1, it becomes obvious that the unusual scenario
of dipole-dipole coupled Feshbach resonances in Li+Na is specific to systems with small
reduced mass µ. For combinations of heavier atoms, such as K+Rb, the near-dissociation
vibrational level spacing is small enough such that there will always be the typical, hyperfineinduced Feshbach resonances with range of experimentally achievable fields.
As a result of the revised assignments, the background scattering length is now abg =76a0 , with E0 /h = 6 Hz, 2×10−5 Hz and 0.015 Hz for each of the three resonances at 745 G,
759 G and 795 G. The strongest resonance from the revised assignment is at 746 G, with an
E0 /h = 5 Hz that is three orders of magnitude smaller than for the earlier assignment, where
the strongest resonance at 790 G had E0 /h = 8 kHz. This small E0 results in a uniquely
challenging situation for molecule formation. Molecule formation experiments with othercomparably weak resonances have been done, but at much lower fields, for example Cs2[Herbig et al., 2003] and 6 Li40 K [Spiegelhalder et al., 2010]. Thus, the combination of
extraordinarily weak coupling, at high magnetic field, in a mixture of two atomic species
makes this perhaps the most difficult Feshbach resonance around which molecule formation
has been successful.
The bound-state open-channel character only for magnetic fields B around resonanceBres such that B − Bres < E0 /∆µ = 2 µG (Section 3.3). This is impossible to resolve experimentally, and precludes molecule formation via radio-frequency association [Zirbel et al.,2008b] or modulation of the magnetic field at a frequency resonant with the molecular binding energy [Thompson et al., 2005], both of which require a large open-channel contribution
for good wave-function overlap between atomic and molecular states. This leaves magnetic
field sweeps across resonance as the only feasible approach.

51

Chapter 4. Formation of 23 Na6 Li Molecules

4.2

Experimental Machinery

The machine we use to produce an ultracold mixture of 6 Li and 23 Na atoms for molecule
formation experiments has been described in great detail elsewhere.1 In brief, we produce
a near-degenerate mixture of 23 Na atoms in the 2 S1/2 |F, mF i = |2, 2i state and 6 Li atoms
in the 2 S1/2 |3/2, 3/2i state in a cloverleaf magnetic trap, by evaporatively cooling 23 Nawith radio-frequency spin flips |2, 2i → |1, 1i tuned to be in resonance with the Zeeman
shifted frequencies of atoms at the very edges of the magnetic trap. The 6 Li atoms are
sympathetically cooled by thermalizing collisions with the 23 Na. At the end of evaporation,
the Li+Na mixture is transferred into a 5-W single-beam optical dipole trap at 1064 nm. In
the optical trap we spin-flip both species with simultaneous Landau-Zener radio-frequency
sweeps at a small bias field of 15 G to the hyperfine ground states Na |1, 1i and Li |1/2, 1/2i.
Note that whereas at low fields |F, mF i is a good basis, at higher fields, when the Zeeman
shift becomes larger than the hyperfine splitting, a good basis becomes |ms , mi i. The
hyperfine ground states at high field are thus Na |−1/2, 3/2i and Li |−1/2, 1i. These aresometimes written simply as Na |1i and Li |1i.
With a Li+Na mixture confined in an optical dipole trap, we use a set of Helmholtz
coils to produce the large, uniform magnetic bias fields required to reach the nearest Feshbach resonances. The narrowness of the resonances in Li+Na places stringent demands onmagnetic field stability for molecule formation. Experimentally we achieve <10 mG rootmean-square (rms) magnetic field noise. The power supply produces current fluctuations
corresponding to 200 mG of noise at 745 G. Active feedback stabilization of the current
reduces the noise to < 10 mG rms after synchronizing experimental sequences with the
60-Hz line frequency. Further details on the magnetic field stabilization in our experimentcan be found in [Christensen, 2011].
1

The original construction of the ultracold atoms machine as a Na Bose-Einstein condensate experimentis described in [Chikkatur, 2002], with further details found in [Pasquini, 2007] and Shin [2006]. The machine
was later upgraded to be a dual-species, 23 Na + 6 Li apparatus, based on the original design in [Hadzibabic,
2003]. Details for the various components of the upgraded machine can be found in [Jo, 2010], [Christensen,
2011], [Lee, 2012], and [Notz, 2014]

52

Chapter 4. Formation of 23 Na6 Li Molecules
For the rest of the experiments described in this chapter, we work around the strongestof the experimentally accessible Feshbach resonances, at 745 G. From low magnetic field, we
first jump far above resonance to 752 G, and after waiting 200 ms the mixture is evaporatively cooled by lowering the intensity of the trapping beam, leaving 1 × 106 each of Na and
Li at a temperature of 1.2 µK. Here, the weak magnetic field curvature along the optical
dipole trap provides additional axial confinement, giving radial and axial trap frequencies(νr , νz ) of (920 Hz, 13 Hz) for Na, and (2.0 kHz, 26 Hz) for Li. The temperature of the mixture is near the onset of condensation for the bosonic Na, with T /Tc = 1.2, and T /TF = 0.3,
where for our trap parameters the condensation temperature for Na is Tc = 1.0 µK and the
Fermi temperature for Li is TF = 4.1 µK. The peak in-trap densities are 2.5 × 1013 cm−3
for Na and 1.4 × 1013 cm−3 for Li.
The precise location of the 745 G resonance is determined by jumping down to 745.9 G,
waiting 15 ms for the field to stabilize, and then sweeping the magnetic field down at aconstant rate of 50 mG/ms but with a variable end-point. The total atom number remaining
after the sweep drops sharply as the end-point crosses the Feshbach resonance (Fig. 4.2).
This measurement determines the location of the Feshbach resonance to be 745.38 ± 0.04
G, providing a precise target field for molecule formation sweeps. Note the 40 mG widthfrom Fig. 4.2 is not directly related to E0 , Ω or ∆B, but is composed of a number ofcontributions, including three-body loss due to scattering length enhancement, adiabatic
molecule formation, and limitations in magnetic field control.

4.3

Molecule Formation

The experimental sequence we used for successful formation of NaLi is shown in Fig. 4.3.
The start and end points of the magnetic field sweep are chosen to be as close to resonanceas possible while still being outside the region of atom-molecule coupling defined by Ω in
Section 3.5. This maximizes the formation efficiency, because molecules form and begin to
decay immediately after crossing the coupling region around resonance. The initial sweep

53

Chapter 4. Formation of 23 Na6 Li Molecules

Figure 4.2: Determination of Feshbach resonance location. Shown is the remaining atom
number as a function of the endpoint of a downward magnetic field sweep across resonance.
Results are fitted to a hyperbolic tangent function (solid line) with center 745.38 G andwidth 40 mG. The normalized atom number along the vertical axis is a sum of Na and Li
atom numbers, each normalized to 1.
rate was chosen to correspond to ∆LZ = 0.1, which is large enough to result in significant
adiabatic conversion of atom pairs into molecules, but not too large such that in the time
it takes to complete the sweep, molecules will already decay and be lost via collisional
processes.
At the end of the sweep, laser pulses resonant with the 589 nm 2 S1/2 |−1/2, 3/2i → 2 P3/2|−3/2, 3/2i transition in Na and the 671 nm 2 S1/2 |−1/2, 1i → 2 P3/2 |−3/2, 1i transitionin Li remove essentially all of the remaining free atoms from the trap. For closed-channel
Feshbach molecules, the excitation spectrum is sufficiently different from free atoms, so
NaLi molecules are mostly unaffected if the laser pulses are not too long. After a variable
hold time for molecule lifetime measurements, the field is switched above resonance, wherebound molecules rapidly dissociate [Mukaiyama et al., 2004]. Imaging the free atoms gives
us a measure of the molecule number, which for our optimized sweep parameters gives aformation fraction of 5%. This corresponds to a molecule number of 5 × 104 .
To confirm that the detected atomic signal is indeed from dissociated molecules, wecheck that imaging while keeping the magnetic field below resonance gives a negligible signal

54

Chapter 4. Formation of 23 Na6 Li Molecules

Figure 4.3: Experimental sequence for molecule formation. After waiting for the magnetic
field B to stabilize at 745.68 G, we sweep the field across resonance to B = 745.19 G in
800 µs, at a constant rate of 600 mG/ms. At the end of the sweep, simultaneous pulses ofresonant light remove Na and Li atoms from the trap within 100 µs while leaving molecules
unaffected. After a variable hold time for lifetime measurements, molecules are detected by
jumping back above resonance and imaging dissociated atoms. The magnetic field can also
be kept below resonance to confirm that bound molecules are invisible to the imaging light.

Figure 4.4: Absorption imaging of molecular clouds using dissociated Na (a, b) and Li atoms(c, d). The lower images in each pair (b, d) are taken after switching above resonance anddissociating molecules into free atoms. The upper images (a, c) are reference images withthe field below resonance, where free atoms have been removed from the trap and themolecules are invisible to the imaging light.

55

Chapter 4. Formation of 23 Na6 Li Molecules

Figure 4.5: Separation of atoms and molecules in a magnetic field gradient. Absorption
images of (a) free Li atoms, (b) separated clouds of atoms and dissociated molecules, and(c) molecules with free atoms removed, taken 3 ms after release from the crossed optical
dipole trap in a 6 G/cm gradient.
(Fig. 4.4). Below resonance, bound molecules have a vanishing absorption cross section σ
and are invisible to the imaging light, while for free atoms σ is nearly identical to above
resonance because the Zeeman shift produced by magnetic field changes of ∼ 500 mG
is much smaller than the atomic linewidth. A second, independent confirmation of themolecular signal comes from releasing the trapped mixture in a magnetic field gradient, anddemonstrating that the expanding atomic and molecular clouds separate from one another(Fig. 4.5) because of their differential magnetic moment ∆µ. To observe this separation,
we added additional optical confinement along the magnetic field gradient direction, using
a second beam to form a crossed-beam optical dipole trap.
The Landau-Zener parameter in our experiment is estimated from Eq. 3.23 to be δLZ =0.13 by choosing n to be the larger of nNa and nLi . This corresponds to a formation
efficiency of 56%. The discrepancy with the observed molecule fraction of 5% has several
explanations. The simplified Landau-Zener picture in Section 3.5 assumes full phase space
overlap between the atoms involved in molecule formation, which is only true in a BoseEinstein condensate at T = 0 Hodby et al. [2005]; Williams et al. [2006]. In a Bose-Fermi
mixture like NaLi, the phase space overlap is lower, reaching a maximum around the boson
condensation temperature Tc because at lower T the Na condensate begins to have lessspatial overlap with the fermionic Li Zirbel et al. [2008b]. The phase-space overlap between
56

Chapter 4. Formation of 23 Na6 Li Molecules
Na and Li is further reduced because of their different trapping potentials Deuretzbacher
et al. [2008]. Finally, NaLi molecules will form and begin to decay as soon as the magnetic
field crosses resonance. However, due to limitations in magnetic field control, we must take
800 µs to complete the sweep, meaning that a significant fraction of the molecules formed
after crossing resonance will be lost in the remainder of the sweep. We will discuss the
lifetime of NaLi molecules in Section 4.4.

4.4

Optimizing Decay Lifetime

The lifetime of trapped NaLi molecules (Fig. 4.6) can be measured by varying the hold time
before switching the magnetic field above resonance for dissociation and imaging. With
> 90% of both species of remaining atoms removed, the molecular lifetime is 1.3 ms. This
lifetime appears to be limited by collisions with other molecules or leftover atoms rather
than by photon scattering, since it does not increase significantly with reduced intensityof the trapping laser. It can be enhanced by suppressing molecule-molecule collisions in a
3D optical lattice Chotia et al. [2012] and fully removing residual free atoms from the trap.
The molecular lifetime drops to 270 µs when keeping free Na and Li atoms trapped withthe molecules. Finally, if only Li atoms are removed before the hold time and not Na, thelifetime is 550 µs (not shown in Fig. 4.6).
The presence of free atoms increases the molecular decay rate because of inelastic collisions with molecules. Our lifetime measurements show that Na and Li each give comparable
contributions to this increased decay, which is consistent with the constituent atoms in theclosed-channel NaLi molecule being distinguishable from free Na and Li atoms, meaningthat quantum statistics does not play a role in collisions. In contrast, experiments with
open-channel KRb molecules [Zirbel et al., 2008a] showed a sharp dependence of lifetime on
the quantum statistics of the atomic collisional partner. The lifetimes above can also be reported as two-body loss-rate constants βNaLi+Na ∼ 1×10−10 cm3 /s and βNaLi+Li ∼ 4×10−10
cm3 /s. We will treat two-body collisional loss of molecules in greater detail in Section 5.4.

57

Chapter 4. Formation of 23 Na6 Li Molecules

Figure 4.6: Lifetime of trapped NaLi molecules after removing remaining free Na and Li
atoms from the trap (solid squares). Fitting to an exponential gives a decay time constantof 1.3 ms. For comparison, the lifetime without removing remaining free atoms from thetrap is 270 µs (open circles). The normalized molecule number along the vertical axis is asum of Na and Li atom numbers, each normalized to 1 at zero hold time, detected from
dissociating bound NaLi molecules.

58

Chapter 5
Molecules of 6Li2 Around a Narrow Feshbach ResonanceThe contents of this chapter highlight the second scientific contribution of this thesis. Using
the expertise in forming molecules around narrow Feshbach resonances from Chapter 4, weturned our attention to the narrow 543 G Feshbach resonance in 6 Li. As explained in
Section 5.1, there had been a decade-long puzzle about unexpectedly long-lived molecules
formed around this resonance. Our experimental work, described in Section 5.2, conclusively
resolved this puzzle. However, further measurements in Section 5.3 raised a new questionof unexpected behaviour of Li2 +Li collisions, which, as discussed in Section 5.4, deviatedsharply from the simple predictions of the quantum Langevin model. This observation is
explained in Section 5.5, and represents the first example of collisions involving ultracold
molecules explained by physics beyond universal long-range van der Waals interactions.
The work described in this chapter has been published in [Wang et al., 2013].

5.1

A Long-Standing Puzzle in 6 Li

Before the experimental work described in this chapter, there had been a decade-long puzzleof unexpectedly long lifetimes of closed-channel 6 Li2 molecules formed around the narrow
543 G Feshbach resonance [Strecker et al., 2003]. There are two experimentally accessible Feshbach resonances between fermionic 6 Li atoms in their two lowest hyperfine states(Fig. 5.1). One is an extremely wide, open-channel-dominated resonance at 832 G, with59

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach Resonance

Figure 5.1: Feshbach resonances in 6 Li2 . One resonance at 832 G (red) is extremely strong,with an open-channel-dominated region for the bound state that spans the entire 300-G
range of scattering length enhancement. A second resonance at 543 G is much more modest,
and arises from a bound-state that is only weakly coupled to the open-channel. This figure
was taken from [Chin et al., 2010]
abg = −1405a0 , ∆B = 300 G, and an enormous E0 /h = 1012 Hz, meanining that for
B < Bres the bound-state is open-channel dominated for the entire 300 G range of scattering length enhancement [Chin et al., 2010]. The exceptional properties of this resonancearises from the very large background scattering length abg , indicating that the open-channel
spin-triplet scattering potential is already near-resonant, being almost deep enough to havea new bound-state appear at dissociation. This produces the extremely strong coupling
between the open and closed channels. The second resonance at 543 G is more modest,with abg = 60a0 , ∆B = 0.1 G and E0 /h = 240 Hz. This is a closed-channel-dominated resonance, with there being a significant closed-channel component to the bound-state within
0.1 G of Bres .
The 832 G resonance in fermionic 6 Li is almost the perfect realization of the BEC-BCS
crossover described in Section 3.6 [Ketterle and Zwierlein, 2008], with an open-channeldominated region that spans essentially the entire 300-G range of scattering length enhance-

60

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach Resonancement. The first, seminal reports of long lifetimes of bound fermion pairs near this resonance[Cubizolles et al., 2003; Jochim et al., 2003] were quickly explained, as in Section 3.6, interms of Pauli suppression of collisions [Petrov et al., 2004]. The other report, around thesame time, of similarly long-lived bound 6 Li2 molecules around the narrow 543 G Feshbachresonance [Strecker et al., 2003], outside the open-channel-dominated region, had remained
unexplained in the decade since. Around such a narrow resonance, outside the small range
in which the closed-channel bound-state is negligible, there should no longer be any Pauli
suppression of collisions between fully closed-channel molecules. Having previously demonstrated the ability to form molecules around an exceptionally narrow Feshbach resonancein Chapter 4, we decided to revisit the work done around this comparatively much easier
543 G narrow resonance in 6 Li. The idea was that if the closed-channel molecules wereindeed long-lived for some as-of-yet unexplained reason, then they can be evaporatively
cooled to achieve the first example of Bose-Einstein condensation of true closed-channelbound molecules, rather than of long-range halo dimers.

5.2

Molecule Formation Around the 543 G Narrow Resonance

The experimental apparatus used to perform molecule formation experiments in 6 Li is thesame as the one highlighted in Section 4.2. We leave only a pure sample of 6 Li atoms at
the end of evaporative cooling in the magnetic trap by ejecting all remaining Na atoms.
The Li atoms are, as before, transferred into a single-beam optical dipole trap (ODT) withpower 5 W and wavelength 1064 nm. In the ODT we spin-flip Li (|F, mF i = |3/2, 3/2i →|1/2, 1/2i) with a Landau-Zener radio-frequency (rf) sweep at 15 G. Following this, an equalsuperposition of the two lowest Li hyperfine states |1i and |2i (corresponding to |1/2, 1/2i
and |1/2, −1/2i at low field) is prepared by two partially adiabatic rf sweeps at 300 G,
separated by 10 ms. After holding for a further 500 ms, the superposition becomes anincoherent mixture of |1i and |2i. We then further evaporatively cool the Li to T /TF = 0.2,
and transfer the atoms into a second, more weakly confining single-beam ODT parallel to61

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach ResonanceB544.0 G
543.3 G

jump near resonanceimaging
formation sweep
0.6 G/msblast

542.6 G

20 μs

hold time
up to 20 ms
time

Figure 5.2: Experimental sequence for molecule formation. After jumping near the
B = 543 G resonance from above, we sweep B at 0.6 G/ms across a region 1.4 G wide.
Immediately after the sweep, a blast of resonant imaging light removes free Li from thetrap, leaving a pure gas of Li2 . After a variable hold time, remaining molecules are detectedby jumping back above resonance and imaging dissociated free atoms. B can also be kept
below resonance to confirm that Li2 is invisible to imaging light.
the first one, with trap frequencies (νz , νr ) = (21, 480) Hz. Optimized formation of Li2 isdone in this second trap.
Molecules formed out of an incoherent mixture of Li |1i and |2i around the narrow 543 G
resonance are in the highest vibrational state of the spin-singlet potential [Chin et al., 2010].
The initial number in each of |1i and |2i states is 2 × 106 , corresponding to a peak densityof 4 × 1012 cm−3 . A magnetic field sweep across resonance (Fig. 5.2) converts the atoms
into diatomic molecules.
As in Chapter 4, we unambiguously observe the signature of molecule formation by
applying a short blast of resonant imaging light to remove free Li in the |1i state fromthe trap. The small mass of Li means that it will be ejected from the ODT after a single
recoil, and moreover at 543 G the imaging transition is cycling, so a pulse duration of 20µs is sufficient to leave no trace of |1i atoms in the trap. After the blast, imaging the|1i state while keeping B below resonance gives a negligible signal, since Li2 is invisible
to the imaging light here. After switching B above resonance to dissociate Li2 , we image
atoms in the |1i state as a measure of the molecule number, which for our optimized sweep
parameters gives a formation fraction of 10% or a molecule number of 2 × 105 . A second,62

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach Resonance

(a)

(b)

(c)
200 µmFigure 5.3: Absorption images of 6 Li2 molecules. Images of (a) molecules dissociated into
free atoms above the 543 G Feshbach resonance, (b) molecules held below resonance where
they are invisible to the imaging light, and (c) separation of molecules and atoms in magnetic
field gradient.
independent confirmation of molecule formation is obtained by turning on a magnetic field
gradient of 10 G/cm for 6 ms while holding in-trap below resonance, which pushes free Li
atoms away while leaving the spin-singlet molecules unaffected (Fig. 5.3).
For molecule decay measurements, we use two consecutive blasts of imaging light, resonant with |1i and |2i respectively, to remove free atoms in both hyperfine states fromthe trap immediately after the molecule formation sweep. This leaves a pure sample ofLi2 molecules, which undergoes rapid initial decay from their vibrationally excited state,slowing down with increasing hold time in a way that is consistent with two-body decay
from molecule-molecule collisions (Fig. 5.4). The non-exponential nature of the observed
decay rules out that our lifetimes are limited by off-resonant excitations from the trapping
laser, and we have also checked, by holding molecules in trap at up to 8 G below resonance,that decay rates outside the coupling region around resonance are independent of magnetic
field, as expected.
Our measurements demonstrate conclusively that the lifetime of these closed-channelmolecules is in fact short, as expected in the absence of the effects of quantum statistics.
Compared to the previous work, our experiment features magnetic gradient separation as an
unambiguous signal for molecule formation (Fig. 5.3), as well as the ability to remove free63Normalized number

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach Resonance
1.0

0.5

0.0
0

5

10
Hold time (ms)15

20

Figure 5.4: Lifetime of a pure sample of Li2 molecules without free atoms present. The solidline is an exponential fit up to 5 ms hold time, giving decay time constants of 8.7(5) ms,
while the dashed line is a fit to a full two-body decay function.
Li atoms to leave a pure gas of Li2 , both of which were absent from the earlier experiments[Strecker et al., 2003]. The atomic densities and temperatures from our two experiments
are comparable, and thus cannot account for the discrepancy in observed lifetimes.

5.3

Collisions of 6 Li2 with Li and Na atoms

The lifetimes in Section 5.2 were limited by the rate of Li2 molecules colliding with one
another. The molecules are formed in the least-bound vibrational state of the spin-singlet
potential, and any Li2 +Li2 collision that results in vibrational decay of one of the collisionpartners will release enough kinetic energy to eject both from the trap. For the sake ofcompleteness, we also measured how the presence of additional free atoms would affect themolecule decay lifetime. Applying the |1i and |2i-state blast beams (Fig. 5.3) at the endof the hold time instead of immediately after the molecule formation sweep allows us tomeasure molecule decay in the presence of free Li atoms. The small molecule formation
efficiency of 10% means that the density of free Li atoms remaining after the sweep is muchlarger than the molecule density, and thus we expect that the resulting molecular decay
lifetime will be significantly shortened because of the higher density of available collisionpartners.

64Normalized number

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach Resonance
1.0

(a)

0.5

0.0

Normalized number

0

2

4

6

8

1.0

10

(b)

0.5

0.0
0

2

4
6
Hold time (ms)810Figure 5.5: Lifetime of Li2 in the presence of free atoms. (a) Decay with Li (solid squares)is almost identical to the decay of the pure Li2 gas (open circles). (b) Decay with a similar
initial density of Na (solid squares) is significantly faster than the decay of the pure Li2 gas(open circles).
Surprisingly, we instead found that the addition of free Li atoms as collision partners
had only a very small effect on the Li2 lifetime (Fig. 5.5a), as compared to the decay of themolecular sample alone in Fig. 5.4. There should be no Pauli suppression of collisions for
closed-channel Li2 molecules with free Li atoms [Petrov et al., 2004; Regal et al., 2004]. We
confirm this by checking that there is no enhancement of the decay after spin-flipping one
component of Li from |2i to |3i (|F, mF i = |3/2, −3/2i).
When Na instead of Li atoms are trapped with Li2 , significant enhancement of the loss
rate is observed (Fig. 5.5b), as expected, for initial Na densities similar to those of Li. The
Na atoms can be included in the atomic mixture by interrupting the evaporatively coolingsequence near the very end, before all the remaining Na atoms are ejected (Section 5.2). Na
and Li only interact weakly in a mixture, with abg = 14a0 around the 543 G Li Feshbachresonance Schuster et al. [2012]. Thus, the presence of Na has a negligible effect on Li2
molecule formation. The mixture is also produced with comparable temperature and initial
65

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach ResonanceLi2 density as in decay measurements done without Na.

5.4

The Quantum Langevin Model for Collisional Loss

In order to better understand the anomalous collision measurements from Section 5.3, wemust consider a more concrete model for how collisions involving molecules happen at
ultracold temperatures. There exists a simple, universal description for two-body inelastic
collisions and chemical reactions of an ultracold molecule with another molecule or atom
[Gao, 2010; Julienne et al., 2011; Quéméner et al., 2011]. This quantum Langevin model
assumes a large number of available exit channels in the short-range part of the interaction
potential, leading to a unit probability of loss there, and leaving the decay rate dependent
on only the C6 coefficient for the long-range van der Waals interaction between collisionpartners (Fig. 5.6). In particular, for standard two-body decay parametrized by a coefficientβdnj= −βj+k nj nk
dt

(5.1)

where j is an ultracold molecule like Li2 , k is its collision partner (another Li2 molecule, afree atom of Li, or a free atom of Na), and n is the density. The coefficients β for different
partial waves are
4π~
RvdW
µ
24πkB T 3
βp−wave =g
RvdW~
βs−wave =g

2πwith the van der Waals length RvdW = Γ(1/4)
2



2µC6
~2

1/4

(5.2)

, and where the prefactor g = 1 or

2 depending on whether the collision partners are distinguishable or indistinguishable.
The quantum Langevin model has been validated in various experimental settings [Quéméner
and Julienne, 2012], involving heavier alkali molecules like Rb2 [Wynar et al., 2000], Cs2[Staanum et al., 2006; Zahzam et al., 2006], KRb [Ospelkaus et al., 2010], RbCs [Hudson
et al., 2008], and LiCs [Deiglmayr et al., 2011]. We can apply it to the case of collisions
66

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach ResonanceU(r)r-C6 / r6jkr

dnj/dt = – βj+k nj nk

Figure 5.6: Quantum Langevin model for collisions between an ultracold molecule j andanother molecular or atomic collision partner k. Assuming there was such a large numberof available decay states in the short-range part of the interaction potential such that theprobability of loss there is unity, then two-body loss coefficients βj+k reduce to being simple,
universal functions of the C6 coefficient of the long-range part of the potential
Collision Parters
Li2 +Li2
Li2 +Li
Li2 +NaC6 (a.u.)
5580
2970
4253

th
(cm3 /s)βs−wave
7.1 × 10−10
3.0 × 10−10
2.5 × 10−10exp
βs−wave(cm3 /s)
6(2) × 10−10< 5 × 10−114(1) × 10−10

Table 5.1: Two-body decay coefficients for Li2 with different collision partners Li2 , Li, andexp
Na. The theoretical value βs−wave
is taken from the quantum Langevin theory while theexperimental values come from the measurements described in this chapter

involving Li2 by approximating C6 for each pair of collision partners as being the sum of thecorresponding C6 coefficients for all combinations of atom pairs involved Deiglmayr et al.
[2011]. Thus, C6Li2 +Li2 = 4 C6Li+Li , C6Li2 +Li = 2 C6Li+Li and C6Li2 +Na = 2 C6Li+Na . Using
atomic C6 coefficients taken from calculations [Derevianko et al., 2001; Mitroy and Bromley,
2003], we can summarize the results of the quantum Langevin calculations in Table 5.1 andcompare against the experimental results from Sections 5.2 and 5.3. The Li2 +Li collisionshows a striking deviation from the predictions of the quantum Langevin model, and thereason for this will be explained in Section 5.5.
In our experiment, two-body decay of Li2 molecules is described by adding the contri-

67

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach Resonancebutions from Eq. 5.1ṅLi2= −βLi2 +Li2 nLi2 − βLi2 +Li nLi − βLi2 +Na nNa
nLi2

(5.3)

Experimentally, we measure the decay of total molecule number NLi2 rather than nLi2 , so
Eq. 5.1 can be written, assuming separate Gaussian density distributions for Li2 , Li and Na
23/2

ṄLi2
= −βLi2 +Li2 ñLi2 − βLi2 +Li ñLi − βLi2 +Na ñNa
NLi2

(5.4)

with ñ denoting peak in-trap densities. The various two-body decay coefficients β can thus
be extracted from the measurements in Fig. 5.4 and 5.5 by fitting exponential decay rates
at short hold times and normalizing by the initial peak densities. The factor 23/2 accounts
for the variation of density across the trap. The effect of deviations of density profiles fromGaussian is much smaller than the quoted uncertainties for β.
Full expressions for trapped ideal Bose(Fermi) gases in the local density approximation
B T 3/2
are used to calculate peak densities ñNa(Li) = ±( mk) Li3/2 (±z), where m is the mass of
2π~2

the Na(Li) atom, T is the temperature of the gas, and Lin (z) is the n-th order Polylogarithm[Ketterle and Zwierlein, 2008]. We determine T before the molecule formation sweep byfitting Li time-of-flight expanded 2D column density profiles with the fugacity z = eβµ as
a free parameter, giving T /TF = 0.2 or T = 400 nK. After the molecule formation sweep,ñLi is lower by a factor of two compared to before the sweep, despite a molecule conversion
efficiency of only 10%, because many more atoms are associated into molecules that are lost
via collisions with other molecules in the time it takes to complete the sweep.
For the Li2 density, the simplest assumption is that the density distribution is proportional to the Li density profile before the sweep, meaning that ñLi2 can be estimated fromthe ratio of total numbersñLi2 = ñLi NLi2 /NLi

(5.5)

and likewise for the reduced ñLi after the sweep. This is valid if we neglect the complicated68Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach Resonancedensity-dependence of molecule formation efficiency [Köhler et al., 2006] and assume that
Li atoms are selected at random from the Fermi sea to form molecules that do not havetime to reach thermal equilibrium. We improve on this by accounting for the effect ofequilibration. Molecules form with the same average center-of-mass kinetic energy as thefree atoms, but twice the potential energy (due to their larger polarizability). Assuming thatequilibration distributes this excess energy among all the degrees of freedom (according top
the Virial theorem applied to harmonic traps), the cloud width is rescaled by 3/4. In our
experiment, Li2 does not equilibrate along the weak axial trapping direction, so the radialp
cloud diameter is instead rescaled by 7/10. This implies that Eq. (5.5) underestimates
the peak Li2 density by about 30%, which is within the quoted uncertainty of our results,
but we nevertheless include the correction in the analysis. This correction does not apply
to ñLi after the sweep 1 .

5.5

Quantum Depletion and Deviation from Universality

The observed deviation from the predictions of the quantum Langevin model in Li2 +Li
collisions can be explained using a full close-coupling quantum calculation that predicts a
two-body coefficient of 5 × 10−11 cm3 /s for Li2 in the least bound triplet state [Quéméner
et al., 2007]. A similarly low value can be inferred for the least bound singlet state in
our experiment from the same mechanism [Quéméner, 2012]. This effect is called quantum
depletion, and can be explained in terms of the least-bound vibrational state of a molecule
having by far the worst spatial overlap with lower-lying states due to its large spatial extent(Fig. 5.7). In the Li2 molecule, the large vibrational level spacings results in a suppression of
decay in collisions with free Li atoms by quantum depletion. This suppression is absent forcollisions involving heavier alkali molecules, which have smaller vibrational level spacing. It
also is not present in collisions of Li2 +Na and Li2 +Li2 , because these both a higher densityof available decay states in the exit channel [Quéméner and Julienne, 2012; Quéméner et al.,1

Random loss from a Fermi-Dirac distribution leaves the root-mean-square size of equilibrated cloudunchanged

69

Chapter 5. Molecules of 6 Li2 Around a Narrow Feshbach ResonanceLi2 molecule

Li atom

Figure 5.7: Quantum depletion of vibrational decay in molecules. The least-bound vibrational state of a molecule, due to its large spatial extent, has the worst spatial overlap withlower-lying states. For most molecules, however, the density of these lower-lying states is
so large that the molecules still undergo rapidly decay when colliding with free atoms. In
the case of Li2 , its exceptionally large vibrational spacing means there is a very sparse setof decay states, and vibrational decay from the least-bound state in a collision with a free
Li atom is in fact suppressed by quantum depletion
2007; Quéméner, 2012].
In summary, Li2 +Li collisions represent the first example of collisions involving ultracold
molecules determined by physics beyond the simple, long-range van der Waals interactions.
The significance of this is that universal collisions described only by the quantum Langevinmodel do not depend on details of the short-range part of the interaction potential, because
loss is assumed to be unity there. From a chemistry standpoint, it is thus interesting
to search for examples of collisions like Li2 +Li that deviate from universality, because
a number of phenomena involving ultracold molecules, such as scattering resonances orreactivity determined by matrix elements between quantum states, that do depend on the
short-range part of the interaction potential.

70

Chapter 6
Future Directions

To bring this dissertation to its conclusion, I will highlight in this final chapter some of the
future directions that the experimental work in this dissertation has laid the foundations
for. Specifically, I will introduce in Section 6.1 the possibility of transferring the NaLi
molecule to what is anticipated to be the most long-lived spin-triplet ground state among
the heteronuclear alkali atoms. Following this, in Section 6.2 I will briefly describe thetechnique of stimulated Raman adiabatic passage (STIRAP) for transferring weakly-bound
NaLi molecules formed using a Feshbach resonance to their spin-triplet ground state, andthen consider in greater detail the first step of doing photoassociation spectroscopy to map
out the completely unknown electronically excited spin-triplet potentials, in order to find asuitable intermediate state for STIRAP. The chapter will end with Section 6.3 by considering
two scientific opportunities that NaLi molecules in their triplet ground states can unlock:magnetic-field tunability of collisions, and the realization of arbitrary spin Hamiltonians
mediated by spin-rotation coupling in molecules.

6.1

A Long-Lived 23 Na6 Li Spin-Triplet Ground StateFor diatomic molecules consisting of alkali atoms, the ground-state of the spin-triplet potential is a metastable one, and can decay to lower lying spin-singlet states (Fig. 6.1). Whereas
for other molecules this happens too rapidly for the triplet ground-state to be experimentally71

Chapter 6. Future Directions

E

S = 1 ground stateS = 1 ground state

De = 220 cm-1

De = 7050 cm-1
r

Figure 6.1: Spin-triplet and singlet ground states of NaLi. The S = 1 spin-triplet groundstate can decay to lower lying spin-singlet S = 0 states, since the singlet potential is somuch deeper. The dissociation energies De of the potentials are 7050 cm−1 for the singlet
and 220 cm−1 for the triplet [Mabrouk and Berriche, 2008]. The triplet ground state has an
unpaired total electron spin, which can have projections 0 or ±1, while the singlet groundstate has no unpaired electron spins.
useful [Ni, 2009], in NaLi the triplet ground-state is expected to have a considerably longer
lifetime. This triplet ground-state is appealing because of possibility of having a magnetic
moment coming from the unpaired electron spins, along with a small but significant electric
dipole moment of ∼ 0.2 Debye [Aymar and Dulieu, 2005; Mabrouk and Berriche, 2008].
Decay of the spin-triplet ground-state to lower-lying spin-singlet states requires flippingof the electron spin. This can happen via dipolar relaxation or second-order spin-orbit
coupling. Both of these spin-flip terms are common to the collision Hamiltonians of both
molecules and atoms. Dipolar relaxation arises from dipole-dipole coupling between themagnetic dipole moments in each collision partner, and is a negligible contribution to loss
in the smaller alkali atoms, with βdip ∼ 10−14 cm3 /s [Gerton et al., 1999]. Since themagnetic dipole of a triplet ground-state molecule is the same order of magnitude as thatof an alkali atom (S = 1 vs. S = 1/2), dipolar relaxation in molecules will also be similarly
slow [Krems et al., 2009]. Second-order spin-orbit coupling produces spin-flips indirectly
through intermediate excited states with electronic orbital angular momentum. In atoms it
is an effect that grows with increasing nuclear charge Z [Bernath, 2005], and is weaker thandipolar relaxation in the small alkali atoms [Mies et al., 1996]. Since in NaLi the closest
72Chapter 6. Future Directions
excited state with electronic orbital angular momentum is Na(3s)+Li(2p), we expect that
second-order spin-orbit coupling will, as in the case of the bare Li atom, have a negligibly
small effect.
We can estimate the lower-bound for the triplet ground-state lifetime by using thequantum Langevin model from Section 5.4. This assumes the worst-case scenario, thatdipolar relaxation and second-order spin-orbit coupling are still large enough effects toresult in unit probability of loss at short-range. For heteronuclear molecules, there are twocontributions to C6 . The first is the same induced dipole-dipole interactions as in atoms,
via second-order coupling to electronic excited states. The second is a d4 /(6Bν ) term thatcomes from the dipole moment of the molecule, where d is the dipole moment and Bν is therotational constant [Julienne et al., 2011]. Whereas for bigger molecules this second term
becomes the dominant contribution to C6 , for NaLi, with its moderate d and large B0 , its
C6 of 3900 a.u. comes mainly from second-order coupling to electronic excited states, andis the smallest among the heteronuclear alkali molecules [Julienne et al., 2011; Quéméner
et al., 2011]. Since NaLi is a composite fermion, we can use the quantum Langevin modelfrom Section 5.4 to estimate the temperature-dependent p-wave universal two-body loss
rate. At 1 µK, this gives an exceptionally small β = 2 × 10−13 cm3 /s, corresponding to a
lifetime of > 1 s at densities of ∼ 1012 cm−3 .

6.2

Photoassociation Spectroscopy of 23 Na6 Li

The plan for transferring NaLi molecules from the least-bound triplet vibrational state with
two units of rotational angular momentum to the rotational and vibrational ground-stateof the triplet potential is to use two-photon stimulated Raman adiabatic passage (STIRAP) [Ni, 2009]. As shown in Fig. 6.2, STIRAP requires detailed knowledge of both theelectronic ground and excited states involved. The Rabi frequencies Ω1 and Ω2 of eachleg of the STIRAP process depend on the corresponding dipole matrix elements [Steck,2010], which, as described in Section 2.7, scale with the vibrational Franck-Condon over-73

Chapter 6. Future Directions

E

Δ

Ω2

Ω2ph = Ω1Ω2 / ΔΩ1r

Figure 6.2: Stimulated Raman adiabatic passage is a two-photon process for molecular statetransfer. Two laser beams with Rabi frequencies Ω1 and Ω2 connect the initial and final
states respectively to an intermediate state. Both lasers are detuned from the intermediate
state by ∆  Ω1 , Ω2 , and the resulting two-photon Rabi frequency is Ω2ph = Ω1 Ω2 /∆laps between the pairs of states involved. The two-photon Rabi frequency thus becomes√Ω2ph ∼ (hνi |νint i)(hνf |νint i) I1 I2 , where νi , νf and νint are the initial, final, and intermediate
vibrational states, while I1 and I2 are the intensities of each of the two STIRAP beams.
Before performing STIRAP, we must identify a suitable intermediate state with sufficientFranck-Condon overlaps with both initial and final states hνi |νint i and hνf |νint i such thatfor experimentally available laser intensities I1 and I2 , Ω2ph is sufficiently large, in the ∼kHz range, to accomplish the molecular state transfer during the ∼ 1 ms lifetime of NaLi
molecules formed around a Feshbach resonance (Section 4.4). Note that the choice of ∆depends on having sufficiently small off-resonant population of the excited state (Ω1 /∆)2such that the decay rate Γ (Ω1 /∆)2 does not limit the lifetime of molecules in the initialstate. To a good approximation, Γ for the molecular excited state is just the spontaneousemission rate of the excited bare atom. For comparison, STIRAP to the triplet groundstate in 40 K87 Rb was accomplished with moderate laser powers in 25 µs [Ni, 2009]. The
main caveat is that vibrational levels in NaLi are more sparse, as discussed in Section 2.1
and 2.3, which will make it more challenging to find a suitable intermediate state withgood overlap with both initial and final states. Also, note that since the initial molecularstate formed using a Feshbach resonance has two units of rotational angular momentum,
74Chapter 6. Future Directions
the intermediate state must necessarily have one unit of rotational angular momentum
to connect to the final, ro-vibrational ground-state in the triplet potential in a way thatsatisfies electric-dipole selection rules (Section 2.7).
There is currently no existing experimental data on the electronically excited triplet
states in NaLi that might be candidates for an intermediate state in STIRAP. Prior to theexperimental work described in Chapter 4, the only available NaLi molecules have beenabsolute ground-state spin singlet ones, and as mentioned in Section 2.8, efforts using theseto explore the spin-triplet potential via spin-orbit mixing of singlet and triplet electronically
excited states have thus far been unsuccessful [Steinke et al., 2012]. As a result, in order
to identify suitable candidates for an intermediate state in STIRAP, we must perform
spectroscopy of the NaLi triplet potentials for the first time.
Based on Section 2.1, we expect the least-bound triplet excited state to be within∼ 3 GHz of dissociation, with another ∼ 20 GHz to the next bound-state. An initialapproach for finding the first of these states might be photoassociation spectroscopy [Joneset al., 2006; Ulmanis et al., 2012] to associate free atom pairs directly into a molecule inan electronically excited triplet state, thus bypassing the short ∼ 1 ms lifetime of triplet
molecules formed using a Feshbach resonance. Once the first excited state is found, the
LeRoy-Bernstein formula from Section 2.1 contrains the locations of the more deeply-boundnear dissociation states. The entire set of bound-states in a particular triplet potential canthus be iteratively mapped out, with the observation of each state providing updated parameters to the theoretical potential, which then leads to a more precise prediction for thelocation of the next state. The ground-state triplet potential can likewise be mapped out
by two-photon spectroscopy. With the first photoassociation laser for the upward leg Ω1(Fig. 6.2) fixed on resonance (∆=0) with a triplet excited state, the frequency of the second
laser for the downward leg Ω2 can be varied. When this second laser is resonant with avibrational level in the triplet ground-state potential, Autler-Townes splitting of the intermediate state [Steck, 2010] will result in a reduction of the photoassociation signal from thefirst laser [Ni, 2009].
75

Chapter 6. Future Directions
The search procedure for detecting the first photoassociation line might involve holding
a Li+Na mixture in a trap, and sweeping the photoassociation laser in frequency at someconstant rate dν/dt for a time t that is limited by the trap lifetime. In our cloverleaf
magnetic trap, where the trap lifetime is limited only by collisions with residual backgroundgas atoms, a sweep lasting as long as ∼ 10 s is feasible. The frequency range over which
one can sweep in a single search is thus determined by dν/dt, which in turn is fixed by
the duration one must spend within the natural linewidth Γ0 of the transition to produce
a measurable loss of the atomic sample to photoassociation. For simplicity one can justtake Γ0 = 6 MHz, which is the natural linewidth of the bare 6 Li atom. This means that if
PA Γ0= 12 , where
we want to produce 50% loss of atoms in a single frequency sweep, then Γdν/dt

ΓPA is the photoassociation rate, in units of 1/s. Note that we are assuming with thisestimate that the transition Γ0 is not power-broadened, which is the same as staying below
the saturation threshold. This is a good estimate because going beyond the saturationthreshold requires using more photoassociation laser power with diminishing returns.
Consequently, we must understand ΓPA for the Li+Na system in order to devise theappropriate frequency-sweep search procedure. The theoretical maximum for this rate is[Jones et al., 2006]
Γmax
PA ≈

nvrel πk2

(6.1)

where n is the atomic density, k is the scattering wave vector in relative coordinates, andvrel is the relative speed. For photoassociation in a mixture of two different atoms, n canbe taken to be the larger of the two densities. Γmax
PA is sometimes called the unitarity
limit, because it assumes that photoassociation is only limited by the collision rate of theatoms, and with unlimited laser power, every atom pair that collides is converted to an√electronically excited molecule. For Li+Na, if we take k ∼ 2mLi kB T /~, vrel = ~k/mLi , and−1 or Γmax /n = K max ∼ 7 × 10−9 cm3 /s.
n = 1012 cm−3 , then at T = 1 µK, Γmax
PA ∼ 7000 s
PA
PA

This Γmax
PA corresponds to a very large dν/dt = 80 GHz/s. The terms k and vrel wereapproximated as ones corresponding to Li alone, because Li is the lighter atom and therefore76Chapter 6. Future Directions
the much faster moving one on average.
In general, ΓPA depends on the density n, the laser intensity I1 ∝ Ω21 , and the dipole
matrix element between the initial scattering state and the electronically excited boundstate. The last of these depends on abg , which from Section 3.2 determines the amplitude of
the scattering wave function within the range of the interaction potential, and in turn affects
the Franck-Condon vibrational wave-function overlap part of the dipole matrix element.
The dipole matrix element for heteronuclear atom pairs is also significantly smaller than forhomonuclear atom pairs, because from the discussion in Section 2.1, the near-dissociationelectronically excited states of homonuclear atom pairs have much larger spatial extent due
to the 1/r3 form of the potential there, as compared to heteronuclear atom pairs with their
1/r6 potential. Finally, the dipole matrix element is expected to increase for molecules like
NaLi with smaller reduced mass µ [Pillet et al., 1997; Azizi et al., 2004]. This is becauseP
if we sum the modulus squares of the Franck-Condon factors, j hνi |νj i hνj |νi i = 1. For
molecules with smaller µ and hence larger spacings of ro-vibrational states, this meansthat the fixed total weight of the Franck-Condon factors will be distributed over a smaller
number of states.
The Li+Na system has a modest, negative background scattering length abg = −76a0[Schuster et al., 2012]. In many ways it is comparable to the Li+Rb system, which also hasa modest negative background scattering length for various isotope combinations [Marzok
et al., 2009; Deh et al., 2010], and moreover has a similarly small reduced mass µ dominatedby the contribution from Li, meaning that the LiRb molecule also has large ro-vibrational
level spacings. Thus, without more detailed knowledge of the dipole matrix elements in
Li+Na, we can use photoassociation experiments with Li+Rb as a benchmark. The main
qualitative difference between the two systems is that the first electronically excited stateof LiRb corresponds to Li(2s)+Rb(5p), which has stronger spin-orbit coupling due to thelarger nuclear charge Z of Rb.
Recent work on photoassociation of 7 Li+85 Rb at ∼ 1 mK found a photoassociation rate
ΓPA comparable to the theoretical maximum in Eq. 6.1 for a state with binding energy
77Chapter 6. Future Directionsof 15 GHz, with atomic densities of 5 × 109 cm−3 for both components and a saturation
laser intensity of 60 W/cm2 [Dutta et al., 2014]. Moreover, in the low-intensity regime,
they found that the slope of KPA with intensity I1 was 2 × 10−12 (cm3 /s)/(W/cm2 ). For agiven atom pair, this slope is independent of temperature [Jones et al., 2006]. At different
temperatures, with the same initial, low-intensity slope, the saturated, unitarity-limited
max scales as T −1/2 , and the saturation intensity correspondingly has the same T −1/2
KPA

scaling.
In our case of 6 Li+23 Na, the atomic densities are ∼ 1012 cm−3 . If we make the one vitalassumption of comparable dipole matrix elements between Li+Na and Li+Rb, then using
the previous slope of 2 × 10−12 (cm3 /s)/(W/cm2 ) as obtained by [Dutta et al., 2014] for
Li+Rb photoassociation, we find that the saturation intensity at 1 µK as opposed to 1 mK
is 2000 W/cm2 . This corresponds to focusing a 1-W beam down to a radius of 100 µm
to obtain the maximum 80 GHz/s unitarity-limited sweep rate. Suppose we decided to
be far more conservative, and sweep by 800 MHz/s. This would assume that the actual,temperature-independent slope of KPA with I1 is actually a factor of 100 smaller for Li+Na
as compared to for Li+Rb, and consequently the dipole matrix element is also 100 times
smaller. As summarized in [Dutta et al., 2014], for most other heteronuclear alkali atom
pairs studied thus far, the maximum measured KPA has been well within two-orders ofmax .
magnitude of the unitarity limit KPA

Photoassociation near the dissociaton threshold is a competition between the rate ofmolecule formation and the rate of atom loss from off-resonant excitations. The latter ofthese has a rate Γatom = Γ0 (Ω0 /∆0 )2 , where Ω0 is the Rabi frequency derived from the free
atom dipole matrix element, and ∆0 is the detuning from the free atom transition. The
relative rate ΓPA /Γatom increases for photoassociation targeting the more deeply boundstates. One semi-classical model for this considers the fact that as the bond length Re
shrinks for the more deeply bound levels, the photoassociation rate decreases as Re2 if one
imagines that, in a gas with uniform density, each atom looks for a binding partner on asphere with surface area 4πRe2 [Ulmanis et al., 2012]. For a 1/r6 van der Waals potential,
78

Chapter 6. Future Directions−1/3

this means ΓPA ∝ Re2 ∝ ∆0

, meaning that it decreases more slowly with increasing ∆0

as compared to Γatom . Despite its simplicity, this model is fairly robust, since we could
have assumed a much stronger power-law scaling of ΓPA with Re and still obtained thesame conclusion. The two drawbacks of going to more deeply bound states are, of course, anecessarily smaller frequency sweep rate dν/dt for the same density and laser intensity due
to a smaller dipole matrix element for the transition, as well as significantly larger spacing
between adjacent levels.

6.3

New Possibilities with Triplet Ground-State Molecules

The realization of a spin-triplet ground state molecule of NaLi will open up at least three
distinct scientific opportunities. The first of these is the exploration of whether collisions
involving ultracold molecules can be tuned in the same manner as Feshbach resonances
for atoms in Chapter 3 [Tscherbul et al., 2009]. Due to the high density of available decaystates in collisions involving molecules, it is possible that quantum scattering resonances will
overlap, leading to an averaged-over, featureless overall scattering dependence on magnetic
field [Mayle et al., 2013]. However, as we demonstrated in Chapter 5, it is precisely in thesmallest molecules, with the most sparse density of states, that collisional behaviour can
deviate from the assumption of there being an essentially infinite density of available decaystates. For example, collisions of NH and ND molecules with 3 He may already be influenced
by the presence of scattering resonances [Campbell et al., 2009].
A second direction comes from the proposal of [Micheli et al., 2006], that molecules possessing both magnetic and electric dipole moments can be used to access a rich landscapeof spin-Hamiltonians in optical lattices. The novel effective spin-spin couplings are due tospin-rotation coupling within each molecule, together with dipole-interaction-mediated coupling of the rotational states of molecules in adjacent lattice sites. The main experimental
challenge of this proposal is that even for the most dipolar molecules, the dipolar interactionenergy scale in a typical optical lattice Udd ∼ 10 kHz is still orders of magnitude smaller

79

Chapter 6. Future Directions
than typical spin-rotation energy scales γ ∼ 10 MHz, although according to [Micheli et al.,2006], one can still realize designer spin models far away from the strong-coupling condition
Udd = γ, but the effective coupling coefficients, and consequently the resulting splittings,
will be significantly smaller.
The third possibility for future experiments with the NaLi molecule in its spin-triplet
ground state arises from its large rotational constant B. An initially spin-polarized gas ofsuch molecules will become collisionally depolarized via dipole-dipole mixing with rotationallyexcited states that have spin-rotation coupling, with a depolarization rate that scales as
1/B 2 [Campbell et al., 2009]. Spin-triplet ground state NaLi molecules can serve as a testbed for collisional stability of 3 Σ molecules in general, illuminating the effects of rotational
excitation, induced electric dipole moment, etc. on the depolarization rate. The stabilityof spin-aligned molecules against collisional depolarization has far-reaching implications forthe ability to magnetically trap and cool a large variety of chemically interesting molecules
down to quantum-degenerate temperatures.
However, one should keep in mind that, from the recent history of the field of matter at
ultracold temperatures, and in the realm of science in general, the true extent of exciting
possibilities for a new form of matter lies not with what researchers anticipate in advance,
but what they discover after its realization. One can only hope the same is true in the fieldof ultracold molecules, and in particular with NaLi, the smallest of the heteronuclear alkali
molecules.

80Appendix A
Asymptotic Bound State ModelIn this Appendix we include an example Mathematica worksheet for predicting Feshbachresonance locations in the 6 Li+23 Na system using the asymptotic bound-state method. The
open-channel state consists of the atom pair in their lowest hyperfine states, |ms , mI i =
−1
2 1

and

−1 3
2 2

for Li and Na respectively.

The total spin projection mF of thisatom pair is 3/2, so there are a total of eight closed-channel bound states with mF =3
2

that can produce Feshbach resonances in the open channel. Six of these are triplet

Nastates S mS mLi
I mI

1
3
= 1 1 − 1 32 , 1 1 0 21 , 1 1 1 −1
2 , 1 0 1 2 , 1 0 0 2 , and1 − 1 1 32 , while two of them are singlet states 0 0 0 23 and 0 0 1 12 .
The Hamiltonian from Eq. 3.18 has matrix elements given in [Walraven, 2010]. The
hyperfine constants and gyromagnetic ratios of the atoms are known [Arimondo et al.,1977], while the triplet and singlet vibrational state binding energies E1 and E0 are left as
free parameters. The worksheet uses a brute-force search method to find the combinationof E1 and E0 that best matches experimentally observed Feshbach resonance locations.
The result is E1 = 5710 MHz and E0 = 4245 MHz, which gives the locations of the threelowest-field Feshbach resonances as 744.5 G, 763.0 G and 794.7 G. These match up well withthe predictions from full coupled-channel calculations in [Gacesa et al., 2008] of 746.13 G,
759.69 G and 795.61 G, as well as the experimental values from [Stan et al., 2004].
However, despite being in good agreement with the three lowest-field resonances, this81Appendix A. Asymptotic Bound State Model
model for Feshbach resonances is actually incorrect [Schuster et al., 2012], and in particular
the locations of the next observed resonance is ∼ 400 G away from its predicted location
Christensen [2011]. The reason, as discussed in Section 4.1, is that the Feshbach resonances
around 800 G are not produced by the traditional hyperfine coupling of the least-boundclosed-channel state to the open-channel, but by weak dipole-dipole coupling of a J = 2
closed-channel rotating molecular state to the open-channel (J here refers to the rotational
quantum number of the molecule, not the total orbital and spin angular momenta of theatoms). This pathological case is not present in other alkali atom pairs, and thus theworksheet below is still a good example how the simple asymptotic bound-state model can
reproduce the results of a much more elaborate coupled-channel calculation.
This worksheet can be adapted for other atom pairs by changing the atomic constants,
as well as the basis of bound states involved in producing Feshbach resonances in the openchannel. It has been successfully applied to the initial search for Feshbach resonances in
23 Na+40 K, for which the discovery of one resonance location enabled one to constrain thebinding energies, and thus predict where nearby resonances would be. The nearby resonaces
were quickly located based on these predictions, avoiding time consuming searches over wide
magnetic field ranges, and further validating the values chosen for the binding energies E1
and E0 . The full description of resonances in 23 Na+40 K required including coupling between the bound states and the continuum scattering states in the closed channel, due tothe large abg of the triplet potential [Wu et al., 2012]. Including this additional coupling ispossible in the asymptotic bound state model, but goes beyond the scope of the example
worksheet included below.

82 Feshbach resonances Li 1 and Na 1 states  Based on asymptotic bound state model
treated in Elements of Quantum Gases by JTM Walraven 
uB : 1.4;  Bohr magneton in units of MHz  G 
InNa : 3  2;  Nuclear spins of Na and Li 
InLi : 1;
EhfNa : 1771.626  Hyperfine splittings 
EhfLi : 228.2053
AhfNa : EhfNa  InNa  1  2  Corresponding hyperfine constants 
AhfLi : EhfLi  InLi  1  2e : 2.00232  uB  Gyromagnetic ratios Na : 0.00080461  uB
Li : 0.00044765  uB
ETrip :  E1  Singlet and triplet binding energies ESing :  E0
 Matrix element of raising operator j m2 J j m1hbar 
Raisej_, m2_, m1_ : Ifj  m1, 0, Sqrtj  m1 j  m1  1 KroneckerDeltam2, m1  1
 Matrix element of lowering operator j m2 J j m1hbar 
Lowerj_, m2_, m1_ : Ifj   m1, 0, Sqrtj  m1 j  m1  1 KroneckerDeltam2, m1  1
 Multivariable Kronecker delta function 
KrDeltax1_, y1_, x2_, y2_, x3_, y3_ :
KroneckerDeltax1, y1 KroneckerDeltax2, y2 KroneckerDeltax3, y3 Simplified FranckCondon vibrational wave function
overlap for two near dissociation halo dimer states FranckCondonE0_, E1_ : 2 E0 E1 ^ 1  4  Sqrt E0  Sqrt E1In[208]:=

 Term in Hamiltonian coupling singlet S
0 and triplet S1 closedchannel bound states  Using total electron spin  projection,individual nuclear spin  projection basis
S mS mI1 mI2  
HCrossCoupS2_, mS2_, mLi2_, mNa2_, S1_, mS1_, mLi1_, mNa1_ : S1z  S2zahf12 I1z  ahf22 I2z KrDeltaS2, 1, mS2, 0, 1, 1 KrDeltaS1, 0, mS1, 0, 1, 1 
KrDeltaS2, 0, mS2, 0, 1, 1 KrDeltaS1, 1, mS1, 0, 1, 1
AhfNa  2 mNa1 KrDeltamNa1, mNa2, mLi1, mLi2, 1, 1 
AhfLi  2 mLi1 KrDeltamNa1, mNa2, mLi1, mLi2, 1, 1  S1  S2ahf12 I1  ahf22 I2 
Sqrt2  KrDeltaS2, 1, mS2, 1, 1, 1 KrDeltaS1, 0, mS1, 0, 1, 1 
KrDeltaS2, 0, mS2, 0, 1, 1 KrDeltaS1, 1, mS1,  1, 1, 1
AhfNa  4 LowerInNa, mNa2, mNa1 KrDelta1, 1, mLi1, mLi2, 1, 1 
AhfLi  4 LowerInLi, mLi2, mLi1 KrDeltamNa1, mNa2, 1, 1, 1, 1  S1  S2ahf12 I1  ahf22 I2 
Sqrt2 KrDeltaS2, 1, mS2,  1, 1, 1 KrDeltaS1, 0, mS1, 0, 1, 1 
KrDeltaS2, 0, mS2, 0, 1, 1 KrDeltaS1, 1, mS1, 1, 1, 1
AhfNa  4 RaiseInNa, mNa2, mNa1 KrDelta1, 1, mLi1, mLi2, 1, 1 
AhfLi  4 RaiseInLi, mLi2, mLi1 KrDeltamNa1, mNa2, 1, 1, 1, 183

In[210]:=

In[211]:=

 Expression for matrix element between any two closed
channel bound states responsible for causing Li 1  Na 1 resonances 
MatElemS2_, mS2_, mLi2_, mNa2_, S1_, mS1_, mLi1_, mNa1_ : Triplet binding energy ETrip KrDeltaS2, 1, S1, 1, 1, 1 KrDeltamS2, mS1, mNa2, mNa1, mLi2, mLi1  Singlet binding energy ESing KrDeltaS2, 0, S1, 0, 1, 1 KrDeltamS2, mS1, mNa2, mNa1, mLi2, mLi1  Term that does not change spin quantum number S 
KrDeltaS2, S1, 1, 1, 1, 1e mS2  Na mNa2  Li mLi2 Bf KrDeltamS1, mS2, mNa1, mNa2, mLi1, mLi2 
AhfNa  4 LowerInNa, mNa2, mNa1 RaiseS2, mS2, mS1  RaiseInNa, mNa2, mNa1
LowerS2, mS2, mS1  2 mS1 mNa1 KrDeltamS1, mS2, mNa1, mNa2, mLi1, mLi2 
AhfLi  4 LowerInLi, mLi2, mLi1 RaiseS2, mS2, mS1  RaiseInLi, mLi2, mLi1
LowerS2, mS2, mS1  2 mS1 mLi1 KrDeltamS1, mS2, mNa1, mNa2, mLi1, mLi2  Cross coupling between S0 and S1 bound states FranckCondonESing, ETrip HCrossCoupS2, mS2, mLi2, mNa2, S1, mS1, mLi1, mNa1 Construction of Hamiltonian in basis of S
1 entries 16 and S0 entries 7,8 closedchannel bound states MatrixConvn_ : Switchn, 1, 1, 1,  1, 3  2, 2, 1, 1, 0, 1  2, 3, 1, 1, 1,  1  2, 4,
1, 0, 1, 1  2, 5, 1, 0, 0, 3  2, 6, 1,  1, 1, 3  2, 7, 0, 0, 0, 3  2, 8, 0, 0, 1, 1  2
HamiltMatrix : TableMatElemMatrixConvn1, MatrixConvn2, n1, 1, 8, n2, 1, 8
MatrixFormHamiltMatrix

Out[213]//MatrixForm=

 5121.71  2.80219 Bf0.
0.
0.
76.0684
0.

0.

0.

0.

 5488.55  2.80268 Bf
0.
76.06840.
 5855.38  2.80318 Bf
626.36476.0684626.364
 5710.  0.00118994 Bf
542.4470.
0.
 5710.
0.
0.
542.447

4.03653  106

 0.0000287847

0.

0.

0.

4.03653  106

 0.0000332377

7.71477  106

 Plot uncoupled closed
channel bound state energies to more easily see which states are which  PlotHamiltMatrix1,1,HamiltMatrix2,2,HamiltMatrix3,3,HamiltMatrix4,4,HamiltMatrix5,5,HamiltMatrix6,6,HamiltMatrix7,7,HamiltMatrix8,8,Bf,0,2000,PlotPoints100 
In[214]:=bNax_ : e  Na  x  EhfNa;
 Standard change of variables for BreitRabi problem bLix_ : e  Li  x  EhfLi;
 BreitRabi formula for entrance channel energies Li 1  Na 1 energNax_ :  EhfNa  2 2 InNa  1  Na x  EhfNa  2 Sqrt1  bNax  bNax ^ 2;energLix_ :  EhfLi  2 2 InLi  1  Li x  2  EhfLi  2 Sqrt1  2  3 bLix  bLix ^ 2;84

0.0000352539

E1  5710;  Set singlet binding energy based on results of search code below 
E0  4245;  Set triplet binding energy  Before starting executing search below,
play around with E1 and E0 to see what values are sensible 
HamiltMatrix : TableMatElemMatrixConvn1, MatrixConvn2, n1, 1, 8, n2, 1, 8;EigenEnerg  EigenvaluesHamiltMatrix; Visualize where intersections between closedchannels and openchannel are 
PlotEigenEnerg  1000, energNaBf  1000  energLiBf  1000,Bf, 0, 2200, AxesLabel  "BG", "EhGHz",PlotStyle  Blue, Thick, Blue, Thick, Blue, Thick, Blue, Thick,Blue, Thick, Blue, Thick, Blue, Thick, Blue, Thick, Red, Thick,
BaseStyle  FontFamily  "Arial", FontWeight  "Bold", FontSize  20,
AxesOrigin  0,  13EhGHz024Out[245]=

6
8
10
12
500

1000

1500

2000

BG

 Solve for where intersections occur  Predicted triplet resonances from M Gacesa: 746, 760, 796 G 
FindRootEigenEnerg8  energNaBf  energLiBf, Bf, 750
FindRootEigenEnerg7  energNaBf  energLiBf, Bf, 760
FindRootEigenEnerg6  energNaBf  energLiBf, Bf, 800
Out[228]=

Bf  744.516
FindRoot::lstol :The line search decreased the step size to within tolerance specified by AccuracyGoal and PrecisionGoal but was unable
to find a sufficient decrease in the merit function. You may need more than
MachinePrecision digits of working precision to meet these tolerances. Out[229]=
Out[230]=

Bf  763.024
Bf  794.688

85

4

FeshCrossFullLi1Na1Optimized.nb

In[231]:=

Out[231]=

 Locations of two singlet resonances  Predicted resonances from M Gacesa: 1097, 1186 
FindRootEigenEnerg5  energNaBf  energLiBf, Bf, 1100
FindRootEigenEnerg4  energNaBf  energLiBf, Bf, 1200
Bf  1127.83
FindRoot::lstol :The line search decreased the step size to within tolerance specified by AccuracyGoal and PrecisionGoal but was unable
to find a sufficient decrease in the merit function. You may need more than
MachinePrecision digits of working precision to meet these tolerances. Out[232]=

Bf  1222.33

86

 Code for optimizing triplet and singlet binding energies E1, E0 
MinRef  9999;  Initial value for minimization variable 
ETrip0  5700;  Initial values for binding energies ESing0  4200;
 Optimization function  E1c,E0c: search range center for triplet and singlet binding energies respectively  Step1, Step0: number of steps to search in each case  Range1, Range0: range of search in each case  These two define the optimization mesh 
BindEnergOptE1c_, E0c_, Step1_, Step0_, Range1_, Range0_ :
Forx   Step1, x  Step1, x ,Fory   Step0, y  Step0, y ,
E1  E1c  Range1  Step1 x;
E0  E0c  Range0  Step0 y;
HamiltMatrix : TableMatElemMatrixConvn1, MatrixConvn2, n1, 1, 8, n2, 1, 8;EigenEnerg  EigenvaluesHamiltMatrix; For each point in mesh E1, E0,
check how far away the three known resonances are 
MinVar  Bf . FindRootEigenEnerg8  energNaBf  energLiBf, Bf, 750  746 ^2
Bf . FindRootEigenEnerg7  energNaBf  energLiBf, Bf, 760  760 ^ 2 
Bf . FindRootEigenEnerg6  energNaBf  energLiBf, Bf, 800  796 ^ 2;
 Keep a record of which variable led
to solutions that are closest to experimental resonances
IfMinVar  MinRef, MinRef  MinVar; ETrip0  E1c  Range1  Step1 x;
ESing0  E0c  Range0  Step0 y;, MinVar  0 Run optimization function and print results 
BindEnergOpt5700, 4200, 10, 10, 50, 50
PrintETrip0, ESing0;PrintMinRef;FindRoot::lstol :The line search decreased the step size to within tolerance specified by AccuracyGoal and PrecisionGoal but was unable
to find a sufficient decrease in the merit function. You may need more than
MachinePrecision digits of working precision to meet these tolerances. 
FindRoot::lstol :The line search decreased the step size to within tolerance specified by AccuracyGoal and PrecisionGoal but was unable
to find a sufficient decrease in the merit function. You may need more than
MachinePrecision digits of working precision to meet these tolerances. 
FindRoot::lstol :The line search decreased the step size to within tolerance specified by AccuracyGoal and PrecisionGoal but was unable
to find a sufficient decrease in the merit function. You may need more than
MachinePrecision digits of working precision to meet these tolerances. General::stop : Further output of FindRoot::lstol will be suppressed during this calculation. 5710, 4245
13.031487

Appendix B
Temperature and Density Measurements

In this Appendix, I will explain the procedure for measuring the temperature T and density
n of trapped atoms in our experiment. We infer the temperature of trapped 6 Li atoms
by measuring the two-dimensional, column-integrated density profile after time-of-flight,
following [DeMarco, 2001]. The temperature of any 23 Na atoms trapped together with 6 Li
is assumed to be the same, since the two atoms form a very favourable mixture with rapid
thermalization and slow inelastic losses [Hadzibabic et al., 2002]. Given T , the peak density
as well as the density variation across trap can be calculated, assuming that the total atom
number and trap frequencies are known.
The 6 Li column-integrated density profile in time-of-flight can be written as2ñ(x, y) ∝ −Li22yxβµ − σx2 − σy2

!

−e e

(B.1)

where β = (kB T )−1 , µ is the chemical potential, and Li2 (x, y) is the second-order polylogarithm function [Ketterle and Zwierlein, 2008]. The expanded atomic density profile isassumed to have different widths σx and σy along the x and y-directions. In the hightemperature limit, z = 1 and Eq. B.1 reduces to an expression for the classical MaxwellBoltzmann distribution. Thus, measuring the temperature of a degenerate Fermi gas corresponds to measuring the effect of the fugacity eβµ on the density distribution.
Experimentally, we obtain time-of-flight absorption images as shown in Fig. B.1a. These88

Appendix B. Temperature and Density Measurements

(b)

(a)

Figure B.1: Temperature measurement of a 6 Li cloud. (a) Absorption image of Li atoms
after time-of-flight from an optical dipole trap. This image is converted to a two-dimensional
column-integrated density profile, and then fit to a Gaussian to obtain the aspect ratio of
the expanded cloud of atoms. This Gaussian fit is used to perform quadrant and elliptical
averaging of the cloud. (b) The resulting column-integrated density as a function of scaled
radius is plotted (red) and fit to the Polylogarithm function (blue) to obtain the fugacity
are converted to column-integrated density profiles ñ by taking the logarithm of each pixel
value, and rejecting pixels whose values are too close to zero. The two-dimensional profiles
are then fit to Gaussians to obtain the aspect ratio of the expanded cloud. This Gaussian
fit is used to average the density profiles in two ways. First, based on the center of theGaussian fit, each density distribution is averaged by reflecting along the x and y axes ofsymmetry to obtain four identical, averaged quadrants. Second, using the aspect ratio fromthe Gaussian fit, we can obtain elliptical contours along which x2 /σx2 + y 2 /σy2 in Eq. B.1 isconstant. The values of ñ are averaged along each of these ellipses and plotted as a functionof the coordinate along the major axis of the ellipses. The resulting plots are fitted to the22function ñ(r) = A Li2 (eβµ e−r /σr ) to obtain the fugacity eβµ , where r can be thought of as
an effective radius for the ellipse, scaled to the major axis.
An example of such a fit is shown in Fig. B.1b, corresponding to βµ = 3.54. From

 
 2
TF
π2
T
the low temperature expansion βµ = T
1 − 12 TF + ... [Lee, 2012], we can solve
for T /TF = 0.27, where TF is the Fermi temperature corresponding to the density at thecenter of the trap. Note that at these low temperatures, the zeroth-order approximation
T /TF ≈ (βµ)−1 = 0.28 is already quite good. The temperature T can be calculated fromthe fugacity eβµ , the total atom number N , and the mean trap frequency ω̄ = (ωx ωy ωz )1/3

89

Appendix B. Temperature and Density Measurements[Ketterle and Zwierlein, 2008]
Nf = −

kB T
~ω̄

3

Li3 (−eβµ )(B.2)

with the subscript f indicating that the equation is valid for fermionic atoms. All the
ingredients of the in-trap density distribution n(~r) in the local-density approximation arethus accounted for [Ketterle and Zwierlein, 2008]

nf (~r) = −where the de Broglie wavelength λdB =1
Li3/2 −eβµ−V (~r)
λdB
q

2π~2
mkB T

(B.3)

and V (~r) is the trap potential that is zerofor ~r = 0 and grows as one goes out from the center of the trap.
In the case of bosonic 23 Na, its temperature T can be assumed to be the same as that3
BTof the fermionic 6 Li. Then from the bosonic counterparts of Eq. B.2 Nb = k~ω̄
Li3 (eβµ )we can infer the fugacity eβµ , and this gives the in-trap density distribution via the bosonic1
counterpart to Eq. B.3 nb (~r) = λdB
Li3/2 eβµ−V (~r) [Ketterle and Zwierlein, 2008]. Obviously, the trapping potential V (~r) and frequencies (ωx , ωy , ωz ) will be different for 23 Na vs.
6 Li because of their different dipole matrix elements.

90Appendix C
The Breit-Rabi Formula

The Breit-Rabi formula is an exact expression for hyperfine state energies of J = 1/2 statesof atoms, in particular the electronic ground states. It is especially useful for calibrating
the magnetic field B in an experiment. Different fields B shift the hyperfine states suchthat transition frequencies between them change. Finding the resonant frequency thatdrives transitions between a particular pair of states thus becomes a measure of the field B
experienced by the atom.
The Breit-Rabi formula is written as [Steck, 2010]

E|J=1/2,mJ ;I,mI i = −

Ehfs
Ehfs
+ gI µ B m B ±2(2I + 1)
2


1/2
4mx
1+
+ x2
2I + 1(C.1)

where x = µB (gJ −gI )B/Ehfs , Ehf s is the hyperfine splitting, m = mI ±mJ , gJ is the g-factor
for total electronic angular momentum, gI is the nuclear g-factor, and the ± corresponds towhether a particular state belongs in the F = I ± 1/2 manifold at zero field. The constantsin Eq. C.1 can be obtained for each atom by consulting [Arimondo et al., 1977]
In the next pages I include Mathematica worksheets for the Breit-Rabi formula for 6 Li,
followed by those for 23 Na.

91

In[35]:=

 Exact BreitRabi calculation for 6Li including nuclear terms   or  root depends on whether state belongs to F
I12 or FI12 manifold at zero field state1x_ :  ehf  6  gI uB x  2  ehf  2 Sqrt1  2  3 bx  bx ^ 2; mJ,mI  12,1 
state2x_ :  ehf  6  gI uB x  2  ehf  2 Sqrt1  2  3 bx  bx ^ 2; mJ,mI  12,0 
state3x_ :  ehf  6  3 gI uB x  2  ehf  2 1  bx;  mJ,mI  12,1 
state4x_ :  ehf  6  gI uB x  2  ehf  2 Sqrt1  2  3 bx  bx ^ 2; mJ,mI  12,1 
state5x_ :  ehf  6  gI uB x  2  ehf  2 Sqrt1  2  3 bx  bx ^ 2; mJ,mI  12,0 
state6x_ :  ehf  6  3 gI uB x  2  ehf  2 1  bx;  mJ,mI  12,
1   mI order reversed  HFS more important than I bx_ : ge  gI  uB  x  ehf;
gI : 4.47654  10 ^  4  Nuclear gfactor for 6Li 
ge : 2  1.001596521869; Electronic gfactor 
uB : 1.39983  Bohr magneton in units of MHzG 
ehf : 228.20527  Hyperfine splitting for 6Li  Energy differences of various ground hyperfine states in MHz 
diff12x_ : state2x  state1x;
diff13x_ : state3x  state1x;
diff23x_ : state3x  state2x;
diff16x_ : state6x  state1x; Calibration of magnetic field in B basedon Li state 1 to 2 RF transition frequency in MHz 
Solvediff12x  75.6575, xx  542.557

 Check approximately what field Li spin flip is done at 
Solvediff16x  262.6, xx   297 648., x  17.269
diff12550.0
75.6821
Plotstate1x, state2x, state3x, state4x, state5x, state6x,
x, 0, 1000, PlotStyle  Red, Red, Blue, Blue, Blue, Blue,
AxesLabel  "BG", "EMHz", PlotRange   2000, 1500,BaseStyle  FontFamily  "Arial", FontWeight  "Bold", FontSize  14,
AxesOrigin  0,  2000

92

EMHz
1500
1000
500
0
500
1000
1500
200

400

600

800

BG
1000

 Frequencies for imaging from ground states to 2P_32 mJ  32 
 Excited state hyperfine splitting very small 
state2px_ :  2 uB x  Excited state shift in MHz 
freqx_ :state2px  state1x  Difference in ground and excited state shifts 
In[50]:=Out[53]=

j1 : 3  2
s1 : 1  2
l1 : 1
 Calculation of gJ for 2P_32 state 
1  j1 j1  1  s1 s1  1  l1 l1  1  2 j1 j1  1  3  2
2freq790
 1022.5
 Mainly useful to obtain how much imaging
frequency changes between different fields freq907  freq795  2
 78.5294

93

In[75]:=

 Exact BreitRabi calculation for 23Na including nuclear terms  Hyperfine state energies in MHz 
state1x_ :  ehf  8  gI uB x  ehf  2 Sqrt1  bx  bx ^ 2; mJ,mI  12,32 
state2x_ :  ehf  8  ehf  2 Sqrt1  bx ^ 2;  mJ,mI  12,12 
state3x_ :  ehf  8  gI uB x  ehf  2 Sqrt1  bx  bx ^ 2; mJ,mI  12,12 
state4x_ :  ehf  8  2 gI uB x  ehf  2 1  bx;  mJ,mI  12,32 
state5x_ :  ehf  8  gI uB x  ehf  2 Sqrt1  bx  bx ^ 2; mJ,mI  12,32 
state6x_ :  ehf  8  ehf  2 Sqrt1  bx ^ 2;  mJ,mI  12,12 
state7x_ :  ehf  8  gI uB x  ehf  2 Sqrt1  bx  bx ^ 2; mJ,mI  12,12 
state8x_ :  ehf  8  2 gI uB x  ehf  2 1  bx;  mJ,mI  12,32 bx_ : ge  gI  uB  x  ehf;
gI  8.04611  10 ^  4;  Nuclear gfactor for Na 
ge  2  1.001596521869;  Electron spin gfactor 
uB  1.39983;  Bohr magneton in units of MHzG 
ehf  1771.62615 Hyperfine splitting of Na in MHz ;
Plotstate1x, state2x, state3x, state4x,state5x, state6x, state7x, state8x, x, 0, 1000,
PlotStyle  Red, Blue, Blue, Blue, Blue, Blue, Blue, Blue,
AxesLabel  "BG", "EMHz",BaseStyle  FontFamily  "Arial", FontWeight  "Bold", FontSize  14,
AxesOrigin  0,  3000

EMHz
2000
1000
0
1000
2000
200

In[85]:=

400

600

800

BG
1000

 Excited state energies easily in Paschen
Back regime described by 7.138 of Steck Quantum and Atom Optics text 
Ahfex  18.534;  Excited state hyperfine constants in MHz 
Bhfex  2.724;
gJex  1.334  Excited state electron total angular momentum gfactor ;

94

In[88]:=

 Variation of excited state energy with magnetic field 
ExStateJt_, mJ_, It_, mI_, x_ : Ahfex mI mJ 
Bhfex

9 mI mJ2  3 Jt Jt  1 mI2  3 It It  1 mJ2  It It  1 Jt Jt  1uB gJex mJ  gI mI x;

4 Jt 2 Jt  1 2 It  195



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