Structure and spectroscopy of candidates for anelectron electric dipole moment experiment
byEdmund R. Meyer
B.Sc., University of Washington, 2004 (Physics)
B.Sc., University of Washington, 2004 (Astronomy)

A thesis submitted to the
Faculty of the Graduate School of the
University of Colorado in partial fulfillmentof the requirements for the degree ofDoctor of Philosophy
Department of Physics
2010This thesis entitled:
Structure and spectroscopy of candidates for an electron electric dipole moment
experiment
written by Edmund R. Meyer
has been approved for the Department of Physics

John L. Bohn

Chris H. Greene

Date

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

iii
Meyer, Edmund R. (Ph.D., Physics)
Structure and spectroscopy of candidates for an electron electric dipole moment experiment
Thesis directed by Prof. John L. Bohn

The identification of suitable diatomic molecules as candidates for an electron
electric dipole moment (eEDM) experiment is presented. A model is derived and developed in order to efficiently and accurately identify possible diatomic molecules. Thismodel gives the magnitude of the effective electric field experienced by an electron at
the site of one of the nuclei in the molecule. In particular, this thesis identifies several
3 ∆ molecules as viable candidates for the eEDM search. In addition, the relevant tools

for doing precision spectroscopy on these molecules are developed. For molecular ionsin rotating trapping fields, a description of geometric phases is presented that reduces
to the common result in the adiabatic limit, but allows for a description of the effect of
atomic and molecular structure on these phases.

Dedication

For my family

v

Acknowledgements

First, I should acknowldege all those people who kept me motivated to stay ingraduate school by going out and doing things outside of physics. I then want to thankmy parents Bob and Diana as well as my siblings Joe, Dave, and Michelle for always
being supportive.
The many members of the Bohn group with whom I have had many useful discussions on science and non-science alike are C. Ticknor, D.C.E. Bortolloti, M. Lara,
R.M. Wilson, S. Ronen, and G. Quéméner.
I have had the pleasure of discussing at length with many experimentalists andtheorists in my time at JILA, all of whom have enhanced my knowledge of physics. Theyare B. Peden, S. Rittenhouse, R. Pepino, Z. Walters, R. Stutz, L. Sinclair, B. Stuhl,
B.C. Sawyer, J. Schlaerth, D. Meiser, B.L. Lev, A.E. Leanhardt, H. Lewandowski, J.
Ye, and E.A. Cornell.
Lastly, I owe a big heap of gratitude to my advisor, J.L. Bohn, for his boundlessenthusiasm for science which is more than a little catching.

viContents

Chapter
1 In the Beginning. . .
1.1

1

Origin of an electron electric dipole moment . . . . . . . . . . . . . . . .

2 Let’s Get Relative

1
12

2.1

Dirac equation: A mini-review . . . . . . . . . . . . . . . . . . . . . . . .

12

2.2

Schiff’s theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

16

2.3

Enhancement factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

20

2.4

Molecular candidates . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

26

3 A diatom is one atom two many

33

3.1

Chemistry acronym school . . . . . . . . . . . . . . . . . . . . . . . . . .

34

3.2

Σ molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

38

3.2.1

Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

38

3.2.2

Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

45∆-type molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

56

3.3.1

Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

59

3.3.2

Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

63

3.3.3

Hyperfine interactions in 3 ∆1 molecules . . . . . . . . . . . . . .

69

3.3.4

3∆

72

3.3

1 molecules in electric and magnetic fields. . . . . . . . . . .

vii
4 Beyond the Geometric Phase

83

4.1

The basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

84

4.2

General spin-j system: A dressed state derivation . . . . . . . . . . . . .

87

4.3

Pure spin-s system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

91

4.4

Structured spin-J system . . . . . . . . . . . . . . . . . . . . . . . . . .

94

4.4.1

Weak magnetic field, ωr  ωZ  ∆ . . . . . . . . . . . . . . . .

97

4.4.2

Strong magnetic field, ω1 , ω2  ∆  ωr . . . . . . . . . . . . . . 100

4.5

Polar molecules in a rotating electric field . . . . . . . . . . . . . . . . . 102

4.6

3∆

1 molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5 . . . In the End

106
113

5.1

A mild review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

5.2

The future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

Bibliography

115

Appendix
A Sample molpro input

122

B Pure S appendix

128

viii

TablesTable
2.1

Survey of effective electric field for various candidates . . . . . . . . . .

31

ix

FiguresFigure1.1

eEDM at 4 Loop Order . . . . . . . . . . . . . . . . . . . . . . . . . . .

5

1.2

eEDM at 1 Loop Order . . . . . . . . . . . . . . . . . . . . . . . . . . .

7

3.1

YbF potential energy surface . . . . . . . . . . . . . . . . . . . . . . . .

39

3.2

YbF σ molecular orbital . . . . . . . . . . . . . . . . . . . . . . . . . . .

42

3.3

RbYb potential energy surface . . . . . . . . . . . . . . . . . . . . . . .

44

3.4

RbYb σ molecular orbital . . . . . . . . . . . . . . . . . . . . . . . . . .

44

3.5

Hund’s case (b) coupling scheme . . . . . . . . . . . . . . . . . . . . . .

47

3.6

Transition of interest in 2 Σ . . . . . . . . . . . . . . . . . . . . . . . . .

55

3.7

Hund’s case (c) coupling scheme . . . . . . . . . . . . . . . . . . . . . .

57

3.8

HfF+ and ThF+ potential energy surfaces . . . . . . . . . . . . . . . . .

62

3.9

Hund’s case (a) coupling scheme . . . . . . . . . . . . . . . . . . . . . .

64

3.10 Stark effect in 3 ∆ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

79

3.11 Transition of interest in 3 ∆1 . . . . . . . . . . . . . . . . . . . . . . . . .

81

4.1

Rotating field coordinate frames . . . . . . . . . . . . . . . . . . . . . .

86

4.2

Phase accumulated at arbitrary ω r . . . . . . . . . . . . . . . . . . . . .

95

4.3

Avoided crossing in 3 ∆1 . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

Chapter 1

In the Beginning. . .

The universe is asymmetric and I am persuaded that life, as it is known to us, is adirect result of the asymmetry of the universe or of its indirect consequences.
–Louis Pasteur
The remarks of Pasteur seem rather full of foresight. However, it must be taken
into account that these remarks were made long before the discovery of quantum mechanics and the Standard Model (SM) of particle physics. While the asymmetry alluded
to by Pasteur is a requisite step in the formation of life — the clumping of matter into
ever larger aggregations — the asymmetry is a result of the fact that there is evenmatter with which to start the aggregating. The inhomogeneous distribution of matter
is a direct result of the asymmetry between matter and anti-matter, and therefore life
an indirect consequence of this asymmetry. What do you know, Pasteur was right, in a
way.

1.1

Origin of an electron electric dipole moment
A long, long time ago, before galaxies were even a twinkle in the universe’s eye, araging battle was taking place. Particles and anti-particles were created and destroyed
with reckless abandon in a variety of interactions. Their creation and annihilation was
in balance as neither matter nor anti-matter could win favor. Then, at a certain energy

2
scale, a symmetry broke, and the preservation of balance between particle and its antiparticle nemesis was forever shattered. Inside this broken symmetry lies a peculiar
oddity, matter particles such as the electron are more likely to be produced. Matter
now takes the upper hand in the interactions amongst the various particles in nature,and this is what matters for us; for we are here and not the anti-us.
It appears that the matter-anti-matter asymmetry is connected to charge-conjugation(C). From experimental measurements on the decay of the Kaon (see Ref [1]) only the
combination charge-conjugation plus parity (CP) violation has been measured. In addition, CP-violation has been measured in the B-meson system [2]. A CP operation
reverses all the additive quantum numbers as well as the direction, i.e. an electron moving to the right (+x-direction) would become a positron moving to the left (but still in
the +x-direction in this parity swapped universe). Now, a violation of CP causes one
to expect a violation of time-reversal (T). This is because of the expectation that the
product of CPT should always be invariant. This is akin to saying there is no preferred
direction in space, that no matter the mass of the particle at hand its anti-partner has
the same mass, and that all internal quantum numbers are opposite for each. Schwinger
showed (implicitly) that this invariance is implied by having invariance under Lorentz
transformations [3], transformations at the heart of relativity.
Using the requisite knowledge of the amount of CP violation in the Kaon andB-meson sectors, one can ask whether it is enough to explain the matter to anti-matterasymmetry in the observed universe. If one looked out into the universe and measured
the amount of matter and compared this to the prediction that ensues from the Kaonand B-meson CP violation, she would find that there is still more matter than can be
explained [1]. Thus, one is prompted to search for different forms of CP or T violation. A
natural place to look begins by asking whether fundamental particles have a permanentelectric dipole moment (EDM), or a linear shift in energy with applied electric fields
of arbitrarily small magnitude. Ramsey began searching for the neutron EDM (see

3Ref. [4] for a review on neutron EDMs) and soon the race was on to measure it inelectrons, atoms, muons, neutrinos, and various other composite particles like the Λ 0
and molecules.
Why do EDMs violate T-reversal, and thus CP? The answer lies in the interaction.
Imagine an electron with two spin-axes, one electric and one magnetic. If these axes wereindependent, there would be an introduction of a new quantum number, the projectionof electric spin onto the electric spin-axis. However, given the stability of the periodic
table, i.e. there is no element with 4 electrons in the 1s 2 state, and the Pauli exclusion
principle, it seems fairly safe to proclaim that there is only one spin-axis: the magnetic
spin axis. Therefore, if there is a EDM, it must lie along (or against) this axis. Thus,
an interaction of the form
HEDM = −de σ · E,

(1.1)

would violate T and P symmetries. This is easy to see given that under P, E reverses
sign while under T, σ reverses sign. Thus, P H EDM = T HEDM = −HEDM. Therefore,a measurement of a permanent EDM is evidence for CP violation above and beyond
what is already measured; because CPT is assumed invariant.
Because the electron is of so much interest in this thesis, it is where the search
will begin. Now, the Standard Model (SM) prediction for electron EDM (eEDM) is
extremely small; expected to be about [5, 6]|de | . 10−40 e − cm,(1.2)

a number beyond ridiculously small. Ridiculously small is here defined as being 10 10times smaller than an avid experimenter can measure. An example of a diagram which
contributes to this effect is in Fig. 1.1. The entailed calculation is one that is beyond
my paygrade. Note that wherever the W boson couples to the electron (solid, thickblack line) or quark loop (red triangle) there is a phase associated with the coupling.
This is the phase that leads to parity violation. In order to yield an eEDM, the phase4needs to not vanish at some order in the diagram. It takes four loops in order for theparity violating phase associated with the weak force to not cancel out. Even thoughparity violation exists, near cancellations occur in the calculation which yield a verysmall value for the eEDM. In fact, if the u i and dj (up and down quarks) were of thesame mass, then the eEDM would cancel even to this order [6].
To get a feel for the type of energy shifts this eEDM would produce, it is useful
to see that an atomic unit of electric field (∼ 10 9 V/cm) would produce an energy shiftof 10−31 eV. There is no hope to measure something like this in today’s modern lab.
Fields reachable in the lab (about 4 orders of magnitude less than one atomic unit)
would produce a shift a four orders of magnitude smaller. Thus, why bother to search
for the eEDM?
The fact is that there are many theories which go beyond the SM. Surprisingly(or not so) many of these theories involve interactions with heretofore unseen, massive
particles which do not necessarily obey the rules of CP conservation. These as yet
unobserved particles can give rise to ever larger values of the eEDM because theseparticles may not have the fortuitous cancellation of a parity violating phase that occurs
in the W -boson, quark-loop diagram in Fig. 1.1.
The current experimental limit on the eEDM (d e ≤ 1.6 × 10−27 e cm) is given by
the experiment on the thallium atom [7]. This is a bit shy of the SM prediction. Thereexists a large gap, and it is this gap that theories of physics beyond the SM aim to
fill; let them be called the Theories of the Gap 1 . 12 or so orders of magnitude is a lot
with which to work in a new theory. However, there seems to be a whole smorgasbordof various theories which seem to predict eEDMs in a similar range, a range at or justbelow today’s experimental limits. These new theories are constructed such that the
new particles have masses that are larger than any particle mass yet measured, forotherwise the community would likely have already observed them. Let one of these1

Term coined by J. Schlaerth during beer and billiards

5

Γ
W

ui
W
dj

W
eR

X

W
eL

Figure 1.1: One of many contributions to the eEDM in the SM. The cross denotes
a mass insertion, a technical way to treat the mass of the particle perturbatively. A
right-handed electron, through the many subsequent interactions becomes left-handed.
d (u) denote an up (down) quark while W denotes a weak boson. γ is a photon. Figure
adapted from Ref. [6].

6
new particles be called Y (because, why not) and have a mass m Y .
Instead of trying to write out expressions for the various theories beyond the SM,
it is more instructive to just gain a feel for the size of the eEDM that these theories will
predict. Given the plethora of adjustments to the SM, it seems rather surprising thatmany of these theories give rise to an eEDM that is in the range of 10 −28 –10−30 e cm.
To understand why, in a qualitative sense, it will be beneficial to recall the electron g −2
diagram. This is the electron vertex function. Evaluation can be found in Ref. [8]. Thisis presented in the bottom panel of Fig. 1.2.
The electron g − 2 diagram is well understood, and it can be used to qualitatively
understand the emission and absorption of a large mass, parity violating particle fromthe electron. Fig. 1.2 gives an example of a one loop correction (top panel, (a)) thatwould lead to an eEDM. The phase φ is a CP violating phase associated with thecoupling of an electron to this new particle, the coupling strength of which is f . In theSM, where the exchange of a W -boson does contribute to the electron one-loop diagram,it does not lead to an eEDM at this order due to the cancellation of the phase. Thus, aninteraction of the sort presented in Fig. 1.2 is assumed to couple with a different phaseto left and right-handed electrons denoted e L and eR .
Bickman and DeMille have presented a simple relationship for the size of an eEDM
that particle Y can induce in the electron as compared to the Bohr magneton µ B andg − 2 from such a loop [9, 10]. The heavy particle introduces a propagator ∼ 1/m 2Y .
Because me is the only other mass scale in the problem one argues on dimensional
grounds the diagrams in (a) and (b) of Fig. 1.2 lead to a dimensionless ratiode∝(g − 2)µB



me
mY

2

,

(1.3)

where me is the electron mass. In Gaussian based atomic units it is thus that (notingµB = α/2)   2 
me 2 α2f,de ≈ sin(φ)
c
mY
2π

(1.4)

7

Γ
HaL eEDM

f’ eä Φ

f
eR

eL
Y

Γ
HbL g-2

c

c

e

e
Γ

Figure 1.2: In theories beyond the SM, an eEDM may be generated by a yet unobserved
particle Y. This unobserved particle couples to the different handedness states of theelectron with a phase that is not quite equal, and thus does not completely cancel. This
phase is labeled φ. The top panel (a) is the eEDM inducing interaction with the yet
unseen particle Y . The bottom panel (b) is the electron g − 2 diagram. This diagram
is well known and understood by the physics community. By drawing analogies, it ispossible to express the top panel in terms of known quantities in the bottom panel.

8where (g − 2) = α/π has been used. The reason that many theories predict an eEDM
that is just around the 10−28 –10−30 e cm mark is because from this point forward certain
assumptions will lead to similar estimates. It is often assumed that coupling constants
to the electron will have a similar order of magnitude and thus f /c ∼ 1. The CKM
quark mixing matrix in the SM gives a value of sin(φ) ≈ 1 [11] and one may expect asimilar result to hold in theories beyond the SM. Granted, these are merely assumptions
about the theories, and some do introduce new phases and coupling strengths which canvary due to suppression of CP-violating phases and coupling strengths; this is just to geta feel of the order of magnitude that the eEDM can take. Using these assumptions andthat the mass of the new particle Y is expected to be in the range of m Y ∼100 GeV/c2 –1 TeV/c2 , many theories beyond the SM predict eEDMs around 10 −27 –10−30 e cm,
where mY , the coupling strength ratio f /c, and sin(φ) may each vary by an order ofmagnitude to yield this range. Higher order loops can also contribute, but each loop
is generally reduced in magnitude by a factor α/π and therefore is 10 −3 times smaller
than a one-loop correction.
Thus, there is reason for experimentalists to pursue measurements of the eEDM;
if not just to rule out theories beyond the SM. High energy experiments naturally aim toreach scales comparable to the mass scale of the supposed new particles while table-top
AMO experiments aim to use precision measurements to finagle the eEDM to reveal
itself through tiny shifts in energy. It is the latter which is of concern here.
Sandars showed long ago that an atom can have an electric dipole moment manytimes larger than in the electron itself; an enhancement factor makes the applied field
effectively larger [12, 13]. An electron bearing an EDM will give to the atom an EDM
many times larger. Only the unpaired electron will contribute. The reason is that
an electron that is paired up with another, as in the ground state of the He atom,
will have its spin lie against that of its paired partner thereby negating any effect of aeEDM. This relies on arguments presented earlier above Eq. (1.1). This enhancement

9is the advantage of which the Tl experiment took. In Tl, the enhancement is aroundeff| ≈ 585, a rather large number [5].
| EEapp

Of course, new bounds must always be set and current work on YbF moleculesby the group of Ed Hinds looks to set the new standard [14]. The reason to switch fromatoms to molecules becomes evident when one considers the size of the field required
to go beyond the measurement in Tl. In that experiment the applied field was about
105 V/cm making the effective field roughly 60 MV/cm. In order to go beyond this, one
either needs to increase the applied field, find another atom with a larger enhancement
factor, or move onto molecules. Since the enhancement scales very favorably with theatomic number Z (see Chap. 2 of this thesis and Ref. [5]), Tl is a front runner for atomic
searches. Not many elements are heavier; at least none that are not on restricted lists
and possibly cause bad things to an experimenter’s graduate student(s). Applying larger
fields introduces difficulties with which, being a theorist, I am less familiar. Though, I
can imagine that getting into the many 10s–100s of kV/cm with precision control is adaunting task.
Therefore one moves to molecules. Molecules can have quite large internal fields.
In fact, given the charge transfers and typical molecular sizes, electric fields withinmolecules can be on the order of an atomic unit, or 5 GV/cm. This is a high electricfield laboratory. It is this lab that the Hinds group is using to find the eEDM. In orderto take advantage of such a system one must understand the system. How can one
calculate the size of the effective electric field? Will it really be on the order of an
atomic unit of field? Does bringing in more than one atom complicate the problem?
These questions and so many more are extremely important to answer.
In this thesis I will address the use of molecules as high electric field laboratories
for searching for the eEDM. The motivation to pursue the study of these candidates
is driven by the experimental work in JILA in the group of Eric Cornell [15]. Certain
experimental constraints limit the type of molecules that would be useful. Some of these10
constraints include the ability to easily polarize the molecule. This immediately rulesout homonuclear diatomics. In addition, one wants either small rotation constants or
small Λ-doublets (see Chap. 3 and Ref. [16]). This further limits the search to moleculesthat have large reduced masses or are of a certain class of Hund’s case. Thus, the 10 4
possible combination of diatomics to search through has been greatly reduced to about
102 . Further reduction must come from ingenuity, or an understanding gained from a
few years in graduate school studying molecular systems. It is these years that will bepresented in the next few chapters.
Firstly, one must know whether molecules possess large effective electric fields.
Chapter 2 will address the understanding of the estimation of this quantity. I will use astandard approach that has been modified to include requisite physics to calculate theeffective fields. Some basics of relativistic quantum mechanics will be reviewed. Thena recap of Schiff’s theorem [17] will lead into calculating the effective electric field.
Comparisons will be made to more elaborate calculations.
Chapter 3 will deal with the structure and spectroscopy of diatomic eEDM candidates. A review of the computational methods used will be presented first. The
remaining part of the chapter is broken up into two camps: 2 Σ and 3 ∆ molecules. Eachsection will deal with the structure and then the spectroscopy of each type of molecule.
Because some of the proposed molecules are to be held in ion traps, Chapter 4 willdeal with the additional phase that is introduced by a rotating field. A simple dressedstate formalism will be developed that encapsulates all of the aspects of uniform rotation of a field interacting with a dipole moment, electric with electric and magnetic
with magnetic. The results reduce to that of Berry [18] in the limit of adiabatic rotation. In addition, non-adiabatic corrections as well as the effects of structure will be
addressed in simple examples. The complications that arise for an eEDM experimentin 3 ∆1 molecules will be addressed last.
Chapter 5 will sum up what you are about to read. In addition, some minor

11
improvements that can be made as well as future work with molecules for addressing
physics beyond the SM will be discussed.

Chapter 2

Let’s Get Relative

Although this may seem a paradox, all exact science is dominated by the idea ofapproximation. When a man tells you that he knows the exact truth about anything,
you can be safe in inferring that he is an inexact man.
–Bertrand Russell
Now, let me tell you exactly what I know. As learned in Chap. 1, there is
every reason to expect the electron electric dipole moment (eEDM) to be extremely
small; vanishingly so in the case of the Standard Model (SM). Therefore, it is a great
approximation to use perturbation theory ideas to establish the size of the energy shift
induced by an interaction of an eEDM with the internal electric field in the atom. This
chapter will introduce Schiff’s theorem which states that an electron in an atom will
experience zero total electric field even when a laboratory electric is implied, understandits evasion, understand the size of the effective electric field that interacts with theelectron, and which molecular candidates are best suited for searching out the eEDM
in today’s experiments. But first, a mini-review of the Dirac equation.

2.1

Dirac equation: A mini-review
The Dirac Hamiltonian for an electron in an electromagnetic field can be simply

written~HDirac = βmc2 − eφ + c~
α · (~
p − eA),

(2.1)

13
~ the
where m is the electron mass, −e its charge, p~ its momentum vector and φ and A~ and B~=∇
~ ×A
~ The remaining terms
scalar and vector potential. As usual, E~ = −∇φare matrices

 1 0 
β = 
,
0 −1


 0 ~σ 
α
~ = 
,
~σ 0


~σ 0 
~ = 
Σ

.
0 −~σ

(2.2)

~σ are the Pauli matrices and 1 is the identity matrix. Now, Foldy and Wouthuysen
showed how to transform the odd terms (terms containing α~ ), which connect positive
and negative energy states, into even terms through a series of transformations [19].
For a complete description of all the terms arising in an atom and molecule using suchtechniques, the interested reader is referred to Chap. 3 of Ref. [16].
Hydrogen-like atoms satisfy the following Dirac equation (think of the outermost
electron only)
H0 ψ = (c~α·p~ + βmc2 −Ze2)ψ = Eψ.
r(2.3)

Here, there is only a scalar potential that depends on the magnitude of the separation of
the electron from the nucleus. This equation can be solved using methods in Refs. [20,21]. For purposes here, one is interested in the form of this solution close to the nucleus.
In a many electron atom, “close to the nucleus” means close enough that the electron
sees the unscreened charge 1 of the nucleus, or roughly given by r  a 0 /Z 1/3 , where a0
is the Bohr length. The solution can be written in terms of a radial and angular piece


φ
(r)Ω
njl
jlm


(2.4)
|njlmi = ,ξnjl (r) (−ı~σ · r̂) Ωjlm
1otherwise known as the Full Monty experience

14
where φ and ξ are the large and small parts of the radial wave function, respectively.
The Ω terms are the usual angular functions from angular momentum addition of spinand orbit. They are eigenfunctions of l 2 , lz , s2 , and sz .
In this regime the radial wave functions can be expanded in terms of Bessel
functions that are both regular as r → 0 via
φnjl (r) =ξnjl (r) =icnjl hx(γj + κ)J2γj (x) − J2γj −1 (x)r2cnjl
ZαJ2γj (x),
r

(2.5)
(2.6)

where

8Zr 2
,
x =
a
p
γj =
(j + 1/2)2 − Z 2 α2 ,


(2.7)

κ = (l − j)(2j + 1).

The value of cnjl is determined by requiring that the large component of the radial wave
function should go over to the semi-classical, non-relativistic solution - this is because
the large component is the dominant term when relativity is weak, or when r  a/Zand the electron is well screened from the bare nucleus.
The ordinary, non-relativistic semi-classical solution to the Schrödinger equationisbnl
Rnl (r) = psinr k(r)

Z r

0

0



dr k(r ) + δ .

r1

(2.8)

The value of k(r) is given by the difference of the energy and the modified potential(the potential including the centrifugal barrier) such that2k (r) = 2me(l + 1/2)2
Enl − U (r) −2me r 2



,

(2.9)
2

where U (r) is the electronic potential experienced by the electron. U (r) ≈ − Zer +Pe2
i<j rij , where rij is the separation between two electrons. r 1 is the turning point
while δ is a constant phase. Between the two turning points inside the potential, r 1

15
and r2 , is the dominant contribution to the integral because of the potentials depth.
Ignoring terms beyond the turning point and setting the square of the integral to unity(normalization condition) it is then seen that
Z r

Z r2
Z r2
b2
dr
dr
b2nl
dr 0 k(r 0 ) + δ ≈ nl
sin2
= 1,
k(r)
2
k(r)
r1
r1
r1

(2.10)

where sin2 () has been replaced by 1/2.
Recall the Bohr quantization rule for radial motion which states
Z r2
drk(r) = π(nr + β),(2.11)

r1

where β is a constant. Differentiating this with respect to n r , using k(r) from Eq. (2.9)
and remembering that k(r1,2 ) = 0, yields
Z
dEnl r2 drme= π,dnr r1 k(r)(2.12)and therefore a quick substitution into Eq. (2.10) gives
b2nl =

2me dEnl
2
,
=
π dnr
πa20 ν 3(2.13)

where the outer electron energy has been approximated by
Enl = −

2
Zeff
,
2ν 2

(2.14)

where ν = nr + l + 1 − σl . σl is a quantum defect which accounts for the effects of U (r)on the energy Enl ; thus it accounts for the outer electron whizzing through a cloud ofother electrons as well as the nucleus. It effectively diminishes the principal quantum
number n = nr + l + 1, because the electron when far away sees a charge of unity, but
up close sees the complete nuclear charge. The energy is shifted by the interaction ofthis electron with the remaining cloud around the nucleus.
Zeff takes the value of 1 (2) in neutral (singly ionized) atoms while in a molecule
one can assign a value based on the molecular structure (see Sec. 2.4). The coefficient c njl
can be found by comparing Eq. (2.5) with Eq. (2.8) at distances a 0 /Z  r  a0 /Z 1/3
1/2
 πa 1/2
10
Zeff .
(2.15)
cnjl = sign(κ)
bnl = sign(κ)
2Z
Za0 νl3

16
Quantum Defect Theory is a rich field and the interested reader should look in Ref. [22].
νl is a parameter gained from experimental data on the atom of interest.
The take away message is we can write a form of the radial wave functions atshort distances r  a/Z 1/3 in terms of the nuclear charge Z, the effective charge Z eff ,and a parameter νl .
1/2

1−γj
Z
2Zeff
a0
φnjl (r) = sign(κ)(κ − γj )Γ(2γj + 1) 2Zγj r
a30 νl3
1/2

1−γj

2Zeff
a0
Z
ξnjl (r) = sign(κ)Zα.
Γ(2γj + 1) 2Zγj r
a30 νl3
(2.16)(2.17)

This concludes the brief review of relevant Dirac equation concepts. It is now time to
explore the properties of an interaction involving an electron electric dipole moment(eEDM).

2.2

Schiff ’s theorem
An elementary particle such as the electron, or structured particles such as pro-tons, have this annoying property that when placed in a static electric field they tend todart quickly away. Therefore, in order to measure their EDMs it is necessary to placethem into familiar neutral systems like atoms and molecules. However, this presents a
problem formulated first by Purcell and Ramsey [23] and further expounded upon by
Garwin and Lederman [24].
Imagine applying an electric field E~app to an atom. In equilibrium the electrons
move about to and fro in such a manner that the atom remains at rest, thereby implyingthat the internal electric field E~int acting on each electron (and nucleon for that matter)
exactly balances E~app . Therefore there is no electric field whereby the EDM of theelectron (or nucleon) can interact and create an energy shift. This is the basic conceptof Schiff’s Theorem[17]. Ironically, Schiff’s own paper [17] was more concerned with how
to get around this conundrum. In mathematical terms, this is seen via the following
steps. In the atom, there are particles j with intrinsic electric dipole moments d~j . The

17bare EDM of the atom is thereby the expectation of the sum off all the intrinsic dipolesin the state of interest
hn|

X
j

d~j |ni.

(2.18)In addition, there is an induced dipole moment due to the interaction with E~int . By
writing E~int as the gradient of a potential experienced by the particle,
Hd = −
= −
= ı

X
j

~dj · E~int (rj )

X 1
j

ej

X 1

~ j U (r)d~j · ∇
int

[pj , H0 ] ,ej

j(2.19)(2.20)

where H0 is the Schrödinger Hamiltonian in the absence of EDM terms. In addition, one
assumes the inter particle interactions are solely electrostatic, especially it is assumed
the interactions are independent of p~. H d will cause a mixing of states|ñi = |ni +=X hm|Hd |ni1+ı

En − E m

m

X 1
k

ek

d~k · p~k

|mi
!

|ni,

(2.21)

where here d~k · p~k /ek is a sum over states |mi connected by the interaction and the sum
on k is a summation over the particles. The expectation value hñ|e~r k |ñi, which is the
non-intrinsic dipole moment of the mixed state, is thus
"
#
X
X
X 1
hñ|
e~rk |ñi = hn|ıel~rl ,
d~k · p~k |ni
ek
k
l
k
X
= −hn|
d~k |ni,(2.22)kwhich cancels to first order in Hd the effect of the bare dipole moments in Eq. (2.18).
It is important to note that the application of the the commutation relations used in
Eq. (2.22) requires that the dipole d~k be independent of the velocity of the electron in
the atom or molecule. In that way, one can invoke the commutation relation between ~r l

18
and p
~k to reduce the double sum to one on a single index. This is the heart of Schiff’s
theorem and intrinsically supposes non-relativistic motion of the electron. Thus, it isleft that the total dipole moment of the system is
~ =h
hdi

X

ek ~rk +kXjd~j i = 0,(2.23)and there is no dipole moment, to first order.
However, all is not lost. A common, although “false and misleading,” [25] methodof expressing how the electric field acting on the constituents can be non-zero is to invoke
the following: electrons in the atom are motional, and therefore create a magnetic field.
Thus, there are two internal fields with which to balance the applied electric field thereby
allowing a non-zero effective electric field at the electron within the atom. This is theline of reasoning used by Sandars in the original proposal to search for eEDMs in atoms
in the 1960s [26, 27, 12, 13]. It has been the standard explanation for the evasion of
Schiff’s theorem in many papers since [28, 29, 30, 31]. Basically an assertion is madethat there exists a velocity dependent piece to the force experienced by the electron.
Yet, one can show that the average electric field is still zero, even in the relativistic
sector, i.e. using the Dirac Hamiltonian. The Hamiltonian in Eq. (2.3) combined withthe electron EDM Hamiltonian, which is given by [5]~ · E,~HEDM = −de γ 0 Σ(2.24)~ is the matrix of Pauli matrices on the diagonal (c.f.
where γ 0 is a Dirac matrix and Σ
Ref. [20]), has an expectation value of zero for the electric field. The standard Dirac
Hamiltonian is given by (similar to (2.3) except the electrostatic potential is left as asum of internal and external terms).
H = c~
α · p~ + mc2 γ 0 − e(Φi + Φe ),(2.25)

where α~ is defined in the Sec. 2.1. In addition H has eigenvectors |ψi. The total electric~ i + Φe), where Φi (Φe ) is the internal (external) electrostatic potential.
field is E~ = −∇(Φ

19
A standard approach (c.f [5, 25]) is to separate (2.24) into two parts~ · E~ − de (γ 0 − 1)Σ
~ · E,~HEDM = −de Σ(2.26)

where the first term commutes with Eq. (2.25) and the second term does not. Because
the total electric field is the gradient of an electrostatic potential, it is straightforward
to show that the first term in (2.26) has an expectation value of
h
i
ıde
~
~ · p~, H |ψi = 0,hψ| − de~σ · E|ψi
= − hψ| Σe(2.27)

because |ψi is an eigenstate of H. This is merely a restatement of Schiff’s theorem
because the first term in (2.26) is merely the non-relativistic piece of H EDM . The
second term in (2.26) is responsible for the evasion of Schiff’s theorem, but not because
the expectation value of the electric field is non-zero. In fact, it is straightforward toshow (using Φ = Φi + Φe )1~
E~ = − ∇(eΦ)
eıp, eΦ]= − [~eıp~, (H − c~
α · p~ − mc2 γ 0 ) ,=e(2.28)and since p~ commutes with both α~ ·p~ and γ 0 , it is evident thatı~p, H] |ψi = 0hψ|E|ψi= hψ| [~e(2.29)

because |ψi is an eigenstate of H. Therefore, the average electric field within the atom
is zero.
The true evasion of Schiff’s theorem relies on an invocation (or incantation) ofrelativity: length contraction. As derived in Ref. [25] the dipole moment of the electron
has a different value in the lab frame than in the frame of the atom or molecule. Aftermuch algebra and relativistic quantum mechanics operator identities that are (summarily) executed in [25], one can arrive at an expression for the EDM of the electron in the

20
lab frame:~d~labe = de −γ ~~ ~β de · β.
1+γ(2.30)

β~ is the velocity vector (and not to be confused with the Dirac β in Eq. (2.3) such that~ and γ = (1 − β 2 )−1/2 is the usual relativistic factor with β = v/c. As isp~ = mβγ,
evident, Eq. (2.30) has a velocity dependent piece. Therefore, the assumption made in
Eq. (2.22), namely [~rl , d~j ] = 0, is not valid. The commutation of ~rl with the non-trivial
velocity dependence of the the dipole d~j must be worked out. Therefore, that sum will
not entirely cancel out the bare dipole moments of the constituent particles in the atom.
Therefore, there is a measurable EDM shift in an atom or molecule.
The evasion of Schiff’s theorem is now accomplished. It is the Lorentz contractionof the dipole as it moves relativistically near the nucleus that allows for the non-zero
expectation value of the interaction d~j · E~ while the expectation value of E~ is rigorously
zero. It is standard to interpret the energy shift due to the interaction with the electricfield as arising from an effective electric field E~eff interacting with the dipole momentde . For the rest of this chapter, the concern will be with estimating the size of E~eff .
Therefore, interactions of the form
HEDM = −de~σ · E~eff ,(2.31)

are of interest, where σ is the Pauli matrix for spin and not the version Σ in Eq. (2.2).
Even though the relativity is hidden in the length contraction, and the average fieldin the atom/molecule is still zero, the energy shift will be interpreted as arising froman effective electric field E~eff interacting with electron frame eEDM pointed along thedirection of the magnetic spin axis defined by ~σ .

2.3

Enhancement factor
Sandars [26] noted that the net EDM of an atom can be many times larger thanthe eEDM because of an enhancement of the applied electric field, the enhancement

21
associated with relativity. To get a feel for the size of the electric field necessary, very
simple arguments can be made. First, the electric field experienced by an electron near
the nucleus scales as follows
Eeff ∼

Ze
Z 3e
∼
,
r2
a20

(2.32)

where we use r ∼ a0 /Z because of a0 /Z sets the scale for where all the action happens.
Again, a0 is the Bohr length. Therefore, Eeff scales as Z 3 . The larger the value of Z,
the larger the effective electric field experienced by the electron.
Now, recall the form of the eEDM Hamiltonian in Eq. (2.26). Even in the presenceof multiple electrons in the system, the first term on the LHS of that equation willcontribute zero for the same reasons that it did in Sec. 2.2. The electric field E~ canbe written as the gradient of a potential, and will commute with the many electron
Hamiltonian, even when including electron-electron interactions. It is the second termon the RHS of (2.26) that is of interest. First, notice that it will only contain terms
involving the “small” radial wave function ξ njl (r) because

 0 0 γ0 − 1 = 2 ,
0 −1(2.33)~ = −2~σ The interaction therefore appears as ∼ d e~σ · E~ and involves onlyand (γ0 − 1)Σ
the “small” component of the Dirac wave function. In the non-relativistic limit, thisterm will vanish completely because Zα → 0 when relativity is unimportant.
Now, let there be a wave function |Ψi describing an electron in an atom ormolecule written as a sum of Dirac wave functions |njlmi,
|Ψi =

X
njl

njl |njlmi,(2.34)

where the |njlmi are defined in Eq. (2.4). The parity of each individual solution |njlmi
is given by (−1)l . This, combined with the fact that the electric field is an odd parity
operator will greatly simplify the calculation. Only states with opposite parity will

22
be connected, and the Hamiltonian in Eq. (2.33) acts only on the small component.
Therefore, terms of the form
~ · E|Ψi~hΨ|HEDM |Ψi = −de hΨ|(γ0 − 1))Σ~ small i= −2de hΨsmall |~σ · E|Ψ
~ (~r)|Ψsmall i= 2de hΨsmall |~σ · ∇U
= 2de hΨsmall |~σ · r̂
= 2de

XX

njl n0 j 0 l0Ze2|Ψsmall ir2njl n0 ,j 0 ,l0 hsmall, n0 j 0 l0 m|~σ · r̂Ze2|small, njlmi(2.35)
r2

are important. In the second line the word “small” is to indicate the small componentof the solution, ξnjl (r). From the third to fourth line the potential is assumed to be
dependent on the magnitude of the charge of the nucleus and inversely proportional to
the separation of the electron from the nucleus. This is valid at distances small enoughthat the electron experiences the bare nucleus and it is the dominant contribution to
the potential energy. At larger separations, the potential is screened and relativistic
effects are much smaller due to the smaller velocities involved.
The angular integrand is then going to involve Ω ?jlm (~σ · r̂)3 Ωj 0 l0 m0 , where two
powers of ~σ · r̂ come from the “small” angular components and the other from theinteraction of the spin with the electric field. Due to properties of the Pauli matrices,(~σ · r̂)3 = (~σ · r̂). This is seen using (summation is implied over repeated indexes)(~σ · r̂)2 = ri rj σi σj= ri rj (ıijk σk + δij )(2.36)= ri rj δij + ıri rj ijk σk(2.37)= 1,(2.38)

where the relations ijk ri rj = 0 and ri rj δij is the identity matrix are used. The angular
integral is now given byZΩ?jlm (~σ · r̂)Ωj 0 l0 m0 d(cos(θ))dφ.

(2.39)

23~σ · r̂ is a pseudo-scalar which changes the value of l by one. Recall that pseudo-scalarschange the parity of a state. Thus, for a given state j, the pseudo-scalar will flip l by
one when it flips the parity. Because the pseudo-scalar acts only to change l, j and j 0
must be the same. So, l 0 = l ± 1. When ~σ · r̂ acts on the state Ωj 0 ,l0 ,m0 , it preserves jand changes the parity thereby changing l 0 → l0 ± 1. To evaluate the angular integral,the form of the angular functions for j = l ± 1/2 will be useful (see Ref. [20] for a moredetailed account).
 ϕ+ ;

j = l + 1/2

jmΩjlm =

 ϕ− ; q
ϕ+jm =  q q
ϕ−jm = 

−,(2.41)

.

(2.42)

l+1/2+m2l+1 Yl,m−1/2 
l+1/2−m2l+1 Yl,m+1/2

l+1/2−m2l+1 Yl,m−1/2

q

l+1/2+m2l+1 Yl,m+1/2

m±1/2

ϕ−
jm only exists when l > 0. The Y l(2.40)

j = l − 1/2

jm

where

,

are the regular spherical harmonics and m is

the projection of j. An important identity to use
ϕ+
σ · r̂ϕ−jm = ~
jm .

(2.43)

Note that unless l = j ±1/2 and l 0 = j ∓1/2, the angular integral will be zero. Therefore
the angular integral reduces toZΩ?jlm (~σ · r̂)Ωj 0 l0 m0

=
=

Z

ϕ+
σ · r̂)ϕ−jm (~j 0 m0(2.44)l+1
2l + 1due to the orthogonality and normalization of the spherical harmonics. l takes the value
associated with the j = l − 1/2 term. For an s connected to a p state, l takes the valuel = 1 and the angular integral is 2/3. The angular integration knows that the parity ofthe two states connected by the HEDM must differ.

24
Since one starts out in a given |njlmi in an atom one needs to find the |n 0 jl0 m0 i
states that are connected via the interaction.

The radial piece of the integral in

Eq. (2.35) reduces tohnjl = j ± 1/2|

Ze2
Ze2 0
|n
jl
=
j
∓
1/2i
=
hξ
|
|ξ 0 0i,nj(l=j±1/2)
r2
r 2 n j(l =j∓1/2)
Z r=a0 /Z
Ze2?
=ξnj(l=j±1/2)(r 0 ) 02 ξn0 j(l0 =j∓1/2) (r 0 )r 02 dr 0
r
0
3
2
2
2
4Z α e Zeff.
(2.45)= −γj (4γj2 − 1)(νl00 νl )3/2

which is termed the relativistic enhancement factor. The integrand is only taken to
distances where the unscreened Coulomb charge of the nucleus is present. Beyond thisdistance the integrand is vastly smaller and thus, ignorable. For these small valuesof r the expansions in Eq. (2.17) were used. Therefore, the expectation value of theperturbing Hamiltonian HEDM yields a shift in energy given by2
4Z 3 α2 e2 Zeff
4 X
hΨ|HEDM |Ψi = ∆E = − denl n0 l03
γj (4γj2 − 1)(νl00 νl )3/2
0 0

(2.46)

nl

All that remains is to calculate the  terms.
There is one subtlety to consider. In a molecule, both the p 1/2 and p3/2 electrons
have a projection onto the molecular axis defined by λ. Therefore, one must accountfor this in the angular integrand of Eq. (2.39) where spherical symmetry was assumed.
The p orbital can be expanded into2σ|pi = − √ |p1/2 σi +3r2|p σi.
3 3/2(2.47)

Then one ignores the contribution from the p 3/2 state since it does not preserve thevalue of j. In the end, this introduces a slightly different energy shift for molecules andatoms, which in turn gives a slightly different effective electric field formula. In order tocalculate the effective electric field one takes the energy shift and divides by d e . Thus,

25
the effective electric field for atoms and molecules are given byEeff,atom = −2Z 3 α2 e2 Zeff16s p ,
3 γj (4γj2 − 1)(νns νnp )3/2

2
Z 3 α2 e2 Zeff
16
Eeff,mol = −(σ · λ) √s p
3 γj (4γj2 − 1)(νns νnp )3/2

(2.48)(2.49)In the last line the term σ · λ takes account of the projection of the spin onto themolecular axis defined by λ. It has magnitude 1/2. Therefore, the two are related in√magnitude by 3/2 and this factor accounts for the geometry of the molecular system.
It is a reduction in the size due to projecting onto the lab frame and the molecule frame.
There is an implicit assumption made about the form of the wave function in themolecular system. When the electron is close to the nucleus, one ignores the molecularproperties in favor of the short range atomic ones. Therefore, even in the molecular casethe concern lies with the quantum defects of the atom of interest as well as the effective
charge.
The next section will address calculating  s and p for the molecule. However, it
is instructive to do so for the atom first. In the atom the eEDM interaction does not
mix much in the way of p-orbitals into the ground state. Therefore, one could try toenhance the effect by applying an external electric field and perturbatively couple in
the excited p state (or more generally the excited state of opposite parity). In this limits ≈ 1,(2.50)

p ≈(2.51)

X hs|er̂ · E~app |pi.
E(mp) − E(ns)m

An s-ground state has been assumed and the sum is over all p states connected by theapplied electric field. Were the ground state p in nature then one has  p ≈ 1 and asum over connected s states is required. What is directly evident is that the effective
field in Eq. (2.48) is proportional to the applied electric field E~app , thus defining anenhancement factor. These estimates have been made for many atoms. Two worth
mentioning are Cs [26, 27, 32] and Tl [33, 34]. These papers show that the energy shift

26
in Cs is ≈ 130de Eapp , or that an electric field enhancement of 130 × E app is achieved.
Detailed, fully relativistic calculations yield a value of 114 for the enhancement [32]. In
Tl, the estimate yields −500 [5] while detailed calculations yield −585 [34].
Recall from the introduction (Sec. 1) that Tl is the system in which the current
best limit on the eEDM was attained d e < 4 × 10−27 e-cm [7]. Having quite a large
enhancement of the applied field is the key to this measurement. Yet, it begs thequestion of how to improve on this value. Unfortunately, stable atoms do not get muchheavier than Tl, and therefore the enhancement that grows with Z so favorably comesto an end. And the ability to apply large electric fields is limited in the laboratory to
many kV/cm (perhaps even up to many 10s of kV/cm). One way in which to improveupon this limit is to find systems where s and p orbitals are naturally mixed, or the
spacings of opposite parity levels are vastly closer so a smaller applied electric field gains
in the enhancement factor. Luckily, nature has provided systems where this occurs.

2.4

Molecular candidates
In a diatomic molecule, the atomic orbitals are naturally mixed. s-states mix

with p-states, d with p and f , etc. In so doing, a natural effective electric field is createdin the sense of Eq. (2.49) and this field can be many orders of magnitude larger than isachievable in the laboratory. Within a diatomic molecule an s electron is of particularinterest for eEDM searches. This electron has zero projection onto the molecular axis
(defined by σ) and can be expanded in the following basis
|σi =

lX
max
l=0

l |lσi,(2.52)

where the sum indicates all angular momentum with a zero projection along the molecular axis. This is due to the breaking of spherical symmetry in the molecule. Therefore,pz , d0 , f0 atomic orbitals all contribute to the σ molecular orbital by the argument of
the previous section. This mixing can be interpreted as an effective electric field. l max

27
is the maximum value l can take and will depend on the type of atom being considered. For an alkali-metal atom such as Cs, choosing l max = 2 is sufficient. In order tocalculate the contributions l one must employ ab initio methods. The details of thesecalculations will be developed in the next chapter (3). The important idea here is that√the values of s and p can be quite close to an even mixture, ideally given by 1/ 2 foreach. Moreover, Eeff is independent of the applied field.
Typically, one uses a basis set designed to accurately reproduce atomic data for a
specific atom when performing these calculations. A convenient choice is to use a basis
set that consists of Gaussians. One then centers these Guassian sets on each atom withangular momenta from 0–lmax , the maximum l in the basis. A basis set |bi (the radial
component only) will look like the following
|bi =

X
k

sk |gk i =X

ckl r l e−χkl r

2(2.53)kwhere l is the angular momentum, and the coefficients c and χ will depend on which value
l takes. Thus, an s state is a Guassian, p a first rank polynomial times a Guassian, d asecond rank and so on. When there is a one-electron σ molecular orbital, the molecularwave function can be expressed as|Ψmol i =X
i+chi |sσih i + dhi |pσih i + · · ·Xjc`j |sσj `i + d`j |pσj` i + · · · ,(2.54)

where h and ` are used to signify the heavy and light atom separately. Distinguishing
between h and ` serves to separate out the contribution to  s (p ) from each atom.
Because Gaussians are not necessarily orthogonal to each other, care must be used tonormalize molecular orbitals in the definition of the  parameters. The contribution
from the heavy atom due to s-type orbitals is
P hc hΨmol |sσkh i
s = P k hk? h.
hhjk cj ck hsσj |sσk i(2.55)

28
A similar expression for the p-orbital contribution to the heavy atom isP hd hΨmol |pσkh i
p = P k hk? h.
hhjk dj dk hpσj |pσk i(2.56)The expressions in Eqs. (2.55) and (2.56) do not make a distinction for the principal
quantum number n of the atom, and therefore encompass all the excitations that may
come into play in forming the molecular bond.
Because these expressions give in principle the entire contribution of the the manyns and n0 p excitations, it appears that the definition of the quantum defect parametersνs and νp are harder to define. However, recall that the expression containing ν s andνp in Eq. (2.49) has the origin of these parameters arising from the short range physics
near the nucleus, where the effects of relativity are largest. Therefore, the values of
the quantum defects are still tabulated for the individual atom of interest within themolecule.
In Eq. (2.49) the value of Zeff is not quite as it would be for an atom. In a polar
molecule there is a transfer of charge from one atom to the other. This transfer does notcome in units of the electron charge. A simple model would be to use the measured dipole
moment of a molecule of interest and then use a classical approximation to determine
the amount of charge on the atom of interest. Then, Z eff would be one more than thisnumber because the electron of interest, when far away from this nucleus, would “see”
this charge. Therefore using the system of equations
dmol = r1 q1 + r2 q2(2.57)

Qmol = q1 + q2 ,one can solve for the effective charge on either nucleus. r 1,(2) is the distance from thecenter of mass of the molecule to atom 1 (2). In a neutral molecule Q mol = 0. It is
worth noting that a molecular ion may be of interest since the value of Z eff = qion + 1
can be larger than 2. This further increases the value of the effective electric field. In29order to deal with ions, one must overcome the tendency of ions to dart away in anelectric field. Therefore, a rotating electric field is requisite, and the way in which thisaffects the molecular ions will be addressed in Chap. 4.
There are two other modifications to consider making to Eq. (2.49). In a heavy
molecule there are many configurations of the electron that may participate. For example, in a 3 ∆ molecule (one where there are two units of orbital angular momentum about
the internuclear axis) there are many ways in which the electrons can add up to make∆. There can be a |ππ 0 i configuration as well as a |σδi configuration. Only the latter
will contribute appreciably to the large effective electric field. This is because two π
molecular orbitals involve atomic orbitals of a minimum of p angular momentum. Whilea mixing of p with d orbitals would produce an effective electric field, they would notexperience much of the relativistic enhancement near the nucleus since these orbitals
have minimal amplitude at the nucleus.
In addition, effects such as spin-orbit can connect states with the same total valueof Ω into the state of interest. Ω is the projection of the total spin plus orbital angularmomentum onto the molecular axis. A 2 Σ1/2 molecule will mix with a 2 Π1/2 moleculedue to spin-orbit effects. Thus, a calculation on a heavy (large Z) diatomic in a 2 Σ1/2
state would have to consider the effects of spin-orbit. The 2 Π1/2 would have negligible
contribution to the effective electric field for the same reasons as in the configurations
example. Therefore, there would be a reduction in signal for the 2 Σ1/2 state of interest
due to the spin-orbit interaction.
In Refs. [28, 35, 36] this method was applied to many molecules. To test theeffectiveness of using non-relativistic ab initio software (details of which are presented
in Chap. 3) along with the relativistic enhancements as calculated above, I produced
the values of effective electric fields in Table 2.4. As is evident, the method reproduces
the values of the more extensive calculations to within 25%. Considering that someof the more in depth methods produce values to within a certainty of 10%–25% for30
the effective electric field, the simple method is a nice alternative. The simple method
allows for a quick calculation, taking perhaps a few weeks to complete an in depth studyof the molecular properties and arriving at a value of E eff . More involved methods cantake several months to a year to estimate. For experimental groups looking to choose amolecule for an experiment, the simple method is more than sufficient for determining agood candidate. However, it does not replace the need for a fully relativistic calculation
once a molecule is chosen and/or a measurement is made.
Now that a simple method has been established, it is worth noting the limitations. Firstly, this approach works well for systems where correlation effects between
the electron of interest and the remaining electrons are minimal. Thus, systems with
one to two isolated valence electrons are ideal. While the method can be applied tosystems with many valence electrons, such as WC [42], the number of configurations
begins to take a toll on the time commitment. The accuracy is limited to the diligenceof the graduate student in correctly identifying configurations which would contributeto an effective electric field, since many configurations are necessary.
Also, one may try to improve the method by using multi-channel quantum defecttheory to find the values of the quantum defect parameters ν s and νp of the individual
atoms, i.e. the motion of the electron in the atom of interest [43, 44]. Currently, asingle channel approach is all that is used [44, 27]. However, a multi-channel approachadds time to the calculation without necessarily improving the accuracy. The quantum
defect contains information about the potential the electron experiences when in thecloud of the other electrons. Yet, it is the information about the region near the nucleusthat is most important for these calculations and the essence is already captured in the
single channel method.
Lastly, the fully relativistic calculations need to know information about the wave
function at the site of the nucleus of interest. Therefore, they need hyperfine parameters measured before the calculation can be put of firm footing. This requires going

31

Table 2.1: Effective electric field values produced using the above described method
compared to values produced using more rigorous methods. All values are in GV/cm.
Molecule
BaF
YbF
HgF
PbF
a(1) PbO
HI+
HfF+
ThO
ThF+
RbYb
CsYb
SrYb+
BaYb+
WC

This method
6.1
32
95
-31
23
0.34
30
104
90
-0.7
0.54
-11.3
1.2
54

Fully Relativistic
7.4 [37]
26 [14]99 [38]-29 [38]
26.2 [39]0.34 [40]
24 [41]
N/A
N/A
N/A
N/A
N/A
N/A
N/A

32
back to the board to calculate again after the new information is attained. While thissimple method can be implemented to reevaluate the hyperfine constants, it takes one
down a path of basis set construction which is not at the heart of a speedy calculation.
Therefore, using this method is better suited as a preliminary run that aids the experimentalist in choosing a molecule. The experimenter measures the hyperfine parameters
and then feeds this information to a theorist who uses it to constrain the fully relativistic calculation from the get go, thereby producing a more accurate prediction the firsttime through an extensive calculation.
In principle, the non-relativistic ab initio software can be constrained using thehyperfine information as well. But, one must again ask whether this is going to improve
the overall accuracy compared to the time commitment that would be involved. The
simple method is a powerful way to get you into the ball park quickly and start thegame — with decent accuracy. However, it can only start the ballgame. A strong closer
needs to finish it out in the end. This does not rule out throwing a complete game, it
is just rare in this day and age for the starter to close the game 2 .

2The baseball analogy may have been carried too far

Chapter 3

A diatom is one atom two many

Technical skill is mastery of complexity while creativity is mastery of simplicity– Erik Christopher Zeeman
Let’s get creative. The study of molecular structure and spectroscopy is quite
involved. For many of the molecules presented in Table 2.4 there is no structure orspectroscopic information in the literature. This can make life quite difficult for theexperimentalist. However, life is not so strenuous considering the help that can beafforded by a little physical insight mixed with a healthy dose of creativity — simplicity
by any other name.
In this chapter I will cover the basics of ab initio calculations for gaining insight
into the molecular systems of interest. Even with these calculations, there is quite a bitof uncertainty about the analysis of the spectroscopy. Using perturbative treatments, it
is possible to extract meaningful parameters which govern the dominant spectroscopyof the atoms. Smaller, more detailed effects can then be understood as deviations fromthese dominant terms. A general ab initio procedure will be developed and used tocreate surfaces for the molecules of interest in Table 2.4. Then the basic structure andspectroscopy of these molecules will be discussed in in the following sections.

34

3.1

Chemistry acronym school
Understanding the chemical aspects of heavy diatomic molecules can be a quite

daunting task should one try to incorporate every little detail into the calculation andthen check that no coding errors are found. Even then, approximations have to be madedue to the sheer complexity of the problem. Complexity in science is another way ofsaying it takes a lot of computer time to solve. The more complex a problem is, themore one needs to make assumptions that simplify the problem. Well, that and the factthat most calculations need to be done within the “lifetime” of a graduate student in
the group. Therefore, a natural time limit for the length of the any given calculation isdependent upon weighing the expectations of the student with the professor and trying
to leave enough time to write the work up. Somewhere between 4-12 years possibly 1 .
Luckily, there have been many methods introduced due to the innovations of theoretical and computational chemists and physicists over the years. These innovations
cut down the computational time required to compute molecular properties. While themethods will not give exact properties, they will contain enough information to qualitatively, or more appropriately, ballpark quantitatively describe the system. In what
follows I will walk through the basic steps taken to construct a surface for a diatomic
molecule at the various levels needed to understand the eEDM searches presented in
Chapter 2. All calculations in this thesis are performed with the molpro suite of abinitio codes [45].
As noted in Sec. 2.4 a basis is usually already constructed. In practice, this basis
is described by a set of Gaussian functions |g i i and form an atomic basis set |bj i asfollows|bj i =

Xi

si |gi i.

(3.1)

This set is chosen so as to optimize the properties of the individual atom. As an example,
1

I tried to say 4-8 years but an adviser not to be named said 12

35
for Rb the basis is optimized so as to reproduce the ionization energy of Rb as well as
the polarizability. A good place for obtaining standard basis sets for heavy atoms isgiven in Ref. [46]. Using a a set of atomic bases on each atom, it is now possible todefine a molecular orbital via|φk i =

Xjcj |bj i,(3.2)

where each atomic basis is centered on one of the atoms in the molecule. This is anorbital because it has contributions from all atoms in the calculation, and therefore isslightly different from the basis set definition. A configuration is a product of occupations of orbitals given by|Φl i = AYkdk |φk i.

(3.3)

In a Hartree-Fock (HF) calculation the values of d k can take 0, 1, or 2 for zero, single,
or double occupations of the orbital. A is a shorthand for anti-symmetrization.
For large atoms there is usually another step is reducing the computational time.
While it is conceivable to construct an all electron basis for large atoms such as Ba
and Yb, it is non-practical. Instead, a core potential can be constructed. This core
consisting of N electrons is represented by a pseudo potential. In addition, basis sets
can be constructed at the fully relativistic level. Short of creating a basis for one’s own
use, the quasi-relativistic effective core potentials, which account for a large portion of
the relativistic effects (excluding mass corrections and Darwin-type terms), are a great
tool to use in these calculations. For the atoms of interest in Table 2.4 there are many
great references, chief of which is Ref. [47].
An HF procedure will minimize the energy E of the ground state of the state/symmetry
selected and given occupation numbers. Therefore, only one configuration is optimized
yielding a HF wave function|ΦHF i =

Y
k

dk

X
j

cjk |bj i.

(3.4)

36
The procedure will find the dk and cjk that minimize the total electronic energy E
for the configuration. This procedure is exceptionally fast, however it fails to accountfor the interactions of configurations with each other given that it only optimizes one
configuration.
The next step in the procedure is to build a wave function at the multi-configuration
self-consistent field (MCSCF) level. A thorough discussion can be found in Refs [48,49, 50, 51, 52]. The MCSCF takes as a starting point the optimized electronic energy
E from the HF step as an initial guess. It then finds appropriate linear combinationsof the configurations given in Eq. (3.4) that minimize E over M total configurations.
The M configurations can contain many states of a given symmetry as well as different
symmetries and spin states. This wave function is


Y
X
X
X
ckj |bj i ,|ΦMCSCF i =fl |Φl i =fl  dlk
l

l

k

(3.5)

j

and the procedure finds the fl , dlk , and ckj which minimize the average E; averaged
over all the spin and symmetry states given in the command. Depending on the choiceof active, closed, and frozen spaces this can be a quite time consuming part of theprocedure due to the non-linear optimization routine. An active space is the space inwhich one allows the occupations dlk to be optimized to a any number between 0 and
2 for calculating the average energy. Occupations are no longer required to have zero,one, or two electrons on average; some intermediate number can be used to minimize
the average E.
Deep within the MCSCF is the wave function that contains a configuration (ormany) with the σ-molecular orbital of interest for the eEDM. This orbital mixes s- andp-atomic orbitals to form a molecular orbital |mol, σi. It has an explicit expansion into
Gaussian basis functions according to Eqs. (3.1) and (3.5).
There still remain two steps in developing the total wave function. After computing the MCSCF wave function we move onto an internally contracted, multi-reference

37
configuration interaction (MRCI) procedure [53, 54, 52, 55].
|ΨMRCI i =Xmhm |ΦMCSCF
i,
m

(3.6)

where this procedure finds the hm that minimize the value of E for a given spin multiplicity and space symmetry. The constraint is that the values of f l , dlk , and ckj in
Eq. (3.5) are all fixed to the values determined in the MCSCF procedure. A final stepis the spin-orbit MRCI (SO-MRCI) [56] which is only possible when one uses a basis|bi i that includes the effects of spin-orbit coupling. The SO-MRCI procedure uses single
and multi-electron operators to mix the MRCI wave functions with the constraint thatthe value of Ω, the total projection of all spin and orbital angular momentum onto themolecular axis, is fixed. This procedure does not optimize energies, instead it finds theextent to which the MRCI wave functions are coupled via spin-orbit type interactions.
|ΨSO−MRCI i =Xnln |ΨMRCI
i.
n

(3.7)

The ln are the optimized quantities. As alluded to in Sec. 2.4 the h m and the ln
are parameters which must be factored into the calculation of E eff . They are straightmultiplicative factors because the nominal σ-orbital might get some π-orbital mixed
into it, for example. Appendix A shows how to do all this using molpro.
For systems where there is yet to be any experimental measurement of the molecular properties, the above method is employed at many values of the internuclear separation R. This can be time consuming and a smart choice of the active, closed, and core
spaces must be employed in order to efficiently and effectively produce a set of potential
energy curves. In turn, these curves can then be used to identify the coupling scheme
appropriate for writing down a spectroscopic Hamiltonian. These will be discussed in
the next two sections.

38

3.2

Σ molecules
Many of the proposed searches for the eEDM choose 2 Σ molecules. These molecules

are preferred because of their relative simplicity. In this section I will examine the basic
properties of Σ-type molecules.

3.2.1

Structure
There are two classes of 2 Σ molecules presented in Table 2.4: systems with ap-

preciable charge transfer (YbF, BaF, HgF, and PbF) which are ionically bonded andsystems with little charge transfer (RbYb, CsYb, SrYb + , and BaYb+ ) which are vander Waals bonded. Both types of molecules exhibit the same valence electron characteristics. The single unpaired electron is predominantly comprised of an s-electron fromone of the atoms.
The reason to choose F-containing molecules is fairly clear. Fluorine is quite
adept at taking electrons from atoms. In the case of Yb, Ba, and Hg, the electron taken
comes from the outer ns2 configuration of the heavy atom leaving behind an atomic ns
configuration. n refers to the principal quantum number and in all cases is n = 6 forthe given examples.
In the separated atom limit, the atoms are each neutral while at the minimumof the molecular well, the configuration is more akin to M + F− , where M is a stand-in
for the heavy atom. Therefore, there is a point in the potential energy surface where
F snatches one electron and leads to a location on the surface of an avoided crossing
between the the neutral atom configurations and the ionic ones. An example of a surface
computed at the HF-MCSCF+MRCI level of computation is given in Fig. 3.1 for the
YbF system.
In Fig. 3.1, the black curves represent 2 Σ states while the red curves are 2 Πstates. There are noticeable avoided crossings in this system. Were one to plot vastly

39

E Hunits of cm-1 L

40 000Yb+ +F -20 000Yb H6s6pL+F H2p5 L

0

Yb H6s2 L+F H2p5 L-20 000

2

4

S
6

8
R Hunits of a0 L

10

12

Figure 3.1: YbF potential energy surface calculated at the HF-MCSCF+MRCI level oftheory. The black curves represent 2 Σ states while the red curves represent 2 Π states.
The blue curve is a 1/R plot that shows the Yb + +F− asymptote.

40
more states of 2 Σ symmetry a clear emergence of the “ionic” state Yb + + F− , which lies
around 50,000 cm−1 away in energy, would appear. The blue line in Fig. 3.1 is used to
guide the eye to the 1/R potential that would dissociate to the Yb + + F− asymptote.
The avoided crossing in the ground state occurs around R = 8 a 0 . It is evident that the2 Σ state is well isolated from any other electronic state and therefore is best describedby a set of Hund’s case (b) coupling numbers. More on Hund’s case (b) will be discussed
in the next section.
In the calculation of the potential energy surface the ECP68MDF relativistic
effective core potential with core polarization terms (CPP) and basis were used forYb [57]. For the F atom, the cc-pVDZ basis of Dunning was used [58]. The largetransfer associated with moving an electron from Yb to F results in a rather large
dipole moment of about 4 Debye (D) in the ground state. In the next section I will
discuss the benefits of a large dipole moment.
The general feature to take away from this molecular example is that there is
one unpaired electron around the Yb + ion. This electron, in the free atom, would beof s character alone thus yielding the Σ molecular symmetry in the diatomic orbital.
However, the electron sees a rather large negative charge from the F − ion and tends
to repel from it. This in effect polarizes this electron around the Yb atom mixing thes- and pz -atomic orbitals. It is this mixing that is needed for calculating the effective
electric field Eeff in Eq. (2.49).
The way in which the sign of the effective electric field is defined is based onwhether or not its direction conforms to the electric field along the internuclear axis.
Electric fields point from positive things to negative things. Therefore, a positive effective electric field is one that lines up with the electric field pointing from Yb + to F− in
YbF. Therefore, the unpaired electron around Yb + tends to be pushed by the negative
charge of F− . This causes the free electron to sit on the side of Yb + away from F− ,yielding larger electron density there. This appears as a mixing of the s- and p z -atomic

41
orbitals that has the same effect as an electric field coming from the side of Yb + awayfrom F− . Therefore, the effective electric field is positive. This is borne out by looking at the invention for the dominant configuration in the YbF molecular calculation
performed at the equilibrium position of R e = 3.6 a0 . See Fig. 3.2.
As is evident from Fig. 3.2, there is a large degree of mixing of the s- and p z -typeatomic orbitals around Yb, as evidenced by the asymmetry of the wave function along
the internuclear axis ẑ. This mixing is highlighted by the reddish shading under themolecular orbital curve. The orbital is plotted along the ẑ-axis and is a projection in thexy-plane. Around the F-atom the mixing is much smaller. The atomic configuration isdominated by the p-atomic orbital characteristics. However, there is evidence of somes-atomic orbital mixing due to the slightly smaller peak on one side of F. This leads one
to ask whether the second atom in the diatomic, if it were large enough, can contributeto Eeff .
This leads to a second type of 2 Σ that has been proposed [36]. Where the benefitsof the YbF, BaF, and HgF species have been made apparent, this other species differs.
RbYb and CsYb are vastly different from their Fluoride counterparts. These molecularsystems do not transfer charge nearly as effectively as the Fluorides. This is due tothe relatively similar electronegativities between alkali-metals and Yb. However, Yb isa closed s-shell atom and therefore the only electron in the game is the Rb s-electron.
All other electronic states will be separated in energy by an amount comparable tothe s-p splitting in Rb. In addition, the well separated electronic states can be taken
advantage of when producing the molecular systems. All the atoms considered can be
individually laser cooled to extremely cold temperatures. Applying photoassociation
techniques one can then produce ultracold samples of these molecular systems. This
reduction in temperature would allow for vastly longer coherence times in experimental
efforts.
Where F served to take away an electron, Yb serves to perturb the alkali-metal

42

YbF Sigma Molecular Orbital
0.10

Ψmol @rD

0.05
0.00

F

Yb

-0.05

Eeff HYbL

-0.10
-0.15
-6

-4

-2

0
r HbohrL2

4

6Figure 3.2: YbF σ molecular orbital calculated at the internuclear equilibrium distance.
The wave function is plotted along the axis connecting Yb to F. The blue (red) dot
represents the Yb (F) atom. Notice the asymmetry in the wave function indicating alarger electron density on the side of Yb away from F.

43electron. In the case of Rb and Cs, Yb polarizes the unpaired s-electron. This issimple to see from a van der Waals type argument. Yb and the alkali-metal atomeach induce a dipole moment in the other, altering their wave functions. They becomeslightly distorted, shifting charge in such a way as to attract each other. An alkali-metalelectron, being unpaired, reacts to this induced charge separation on Yb and mixes thes and pz -atomic orbitals along the molecular axis. Yet, the free electron is free to movetoward Yb, and hence while around Yb will react to the charge on the alkali-metal.
In Fig. 3.3 I give a calculation of the RbYb potential energy surface in the ground2 Σ state.

This surface is vastly different than the surface for YbF. First, there is only

one electronic state that dissociates to the separated atom limit of Rb(5s 1 ) + Yb(6s2 ).
The inset in the figure shows a few vibrational levels in the ground electronic state, justin case one could not tell from the figure that the X 2 Σ state is bound. In this calculation
ECP36MDF effective core potential and basis of the Stuttgart group [59, 60] with the
CPP terms were used. A RHF-MCSCF+MRCI calculation was performed at several
points in the internuclear separation between 25 a 0 and 4.5 a0 . The active space included
both the excited p-atomic orbitals for Rb and Yb.
As before, the molecular wave function for the σ-molecular orbital of interest will
identify the s-pz mixing around the individual atoms. This is presented in Fig. 3.4.
The electron has an asymmetric distribution about both atoms, but more so aroundYb. Because Rb and Yb are of comparable size, relativistic enhancements must be
calculated for both. Notice that the direction of the electric field is opposite at the siteof each atom. The more comparable in size the two atoms are, the more the fields tend
to work against each other, creating a net smaller effective electric field. This is seen in
the progression RbYb → CsYb in Table 2.4, where the effective electric field in CsYb
is smaller than in RbYb because Cs in essence steals some of the glory in Yb’s large Z
size.
Another interesting item of note is that the RbYb MRCI calculation shows that

E Hcm-1 L

12

0

10 000

a2 P

32

a2 P

7500

-75

0

Ν=8
Ν=4

12

PA2

5000
2500

RbH5pL+YbH6s2 L

b2 S

12 500

44

9

X 2S

12

6

8

12

Ν=0

-175

10

PA1

X 2S
11

12

RbH5sL+YbH6s2 L

13

10 12 14 16 18 20 22 24
R Hunits of ao L

Figure 3.3: RbYb potential energy surface in the ground 2 Σ state. The calculation was
performed at the RHF-MCSCF-MRCI level of theory.

RbYb Sigma Molecular Orbital

0.02

Eeff HRbL

Eeff HYbL

Rb

Yb

0.01

Ψmol @rD

0.00
-0.01
-0.02
-0.03
-15

-10

-5

0
r HbohrL

5

10Figure 3.4: RbYb σ molecular orbital calculated at the internuclear equilibrium distance. The wave function is plotted along the axis connecting Yb to Rb. The blue (red)dot represents the Yb (Rb) atom. Notice the asymmetry in the wave function indicatinga larger electron density on the side of Yb away from Rb and vice versa on Rb. This
leads to a need to find the value of the effective electric field for both atoms.

45
there are two contributing σ-molecular orbitals, each one dominated by the basis of oneof the atoms. The same scenario holds true for all the molecules of these types; RbYb,
CsYb, SrYb+ , and BaYb+ .

3.2.2

Spectroscopy
Spectroscopy for 2 Σ-type molecules is a well known, and widely studied field.

There is a separation of energy scales that naturally arises in the systems of interest.
Electronic energy separations, the largest in the problem, are of the order 10 5 cm−1 .
These deal with excitations from one electronic state, the 2 Σ, to another like the 2 Π. For
some of the molecules considered, this is a useful bit of information because one way todetect a science signal for the eEDM search is to use transitions from one electronic state
to another. The next scale is molecular vibrations, usually of the order 20–50 cm −1 ,and governs transitions within and between electronic levels. Finally, the next “large”
contribution is from end-over-end rotation of the molecule. This scale is 0.01–10 cm −1 ,depending on the reduced mass and bond length of the system. Further down in energy
are all the various interactions between the constituent spins in the molecule that must
be understood to gain an appropriate understanding of how to do an eEDM experiment.
Molecule based eEDM searches tend to be on the colder side of physics. The
molecules are often studied at temperatures at or below 4 K. For the Fluoride based
molecules this is cold enough freeze out all but the lowest vibrational state and toisolate a few rotational levels within the molecule. Therefore, the dominant terms inthe spectroscopic Hamiltonian will come from rotational pieces.
Because Σ molecules have no orbital angular momentum about the internuclear
axis, they are usually fairly well described by a set of Hund’s case (b) quantum numbers.
In this representation, the spin S is decoupled from the molecular axis N. A semiclassical image of this coupling scheme is presented in Fig. 3.5. In this type of coupling,
the good quantum numbers are N , S, and the vector sum J = N + S in the absence of46
any applied electromagnetic fields. The presence of fields will be addressed shortly.
The basic Hamiltonian for a Hund’s case (b) molecule in 2 Σ can be represented
as follows
H(b) = Bν N2 + γν N · S,

(3.8)

where the subscript ν indicates a particular vibrational level of interest. The termBν is the rotation constant of the molecule. It sets the energy scale of interest in
2 Σ eEDM searches because this is the energy which must be overcome to polarize themolecule, without which the large effective electric fields within the molecule would bemeaningless. Each rotational level has a different parity given by (−1) N .
γν originates from two sources, of which one is far more important for heavy
molecules like YbF. The first order (meaning it arises without the introduction of any
other electronic levels) contribution to the spin-rotation parameter γ ν is given by theinteraction of the magnetic moment of the open shell electrons with the rotational
magnetic moment of the molecule directed along N. This can be thought of as aninteraction akin to the spin-orbit interaction of the electronic spin with the nuclei. The
second order term is given by electronic spin-orbit (electronic spin with electronic orbital
angular momentum) perturbations which couple in excited states of Π-type symmetry.
In heavy molecules, where Z is large for one or both atoms, this is the dominant term.
It has the form [16]γν(2) = −2

X hη, Λ, Σ|Bν L− |η 0 , Λ + 1, Σihη 0 , Λ + 1, Σ| P ai li · si |η, Λ, Σ + 1i + s.o.
iη0(Vη − Vη0 )hS, Σ|S− |S, Σ + 1i

,

(3.9)

where s.o. signifies switching the order of the individual electron spin-orbit operatorP
i ai li · si with the rotation operator B ν L− . η is a stand-in for the other quantum
numbers in the molecules. In Eq. 3.9 I have made explicit the dependence on theindividual electrons. While the expectation value of the total orbital angular momentumis zero, the individual electrons can have orbital angular momentum and this allows

47

J

S
N

Figure 3.5: The Hund’s case (b) coupling scheme vector diagram. The S and N vectors
couple to make the J.

48
communication with excited electronic states via the spin-orbit interaction.
It is not easy to evaluate the matrix elements involving the orbital angular momentum raising and lowering operators L ± and li± . If one of the atoms is vastly larger
than the other, then an approximation can be made called the Van Vleck pure precession hypothesis [61]. The lighter atom is considered a pimple orbiting about the heavier
atom and the electron of interest obeys spherical symmetry about the heavy atom. In
this approximation, the raising and lowering operators act on atomic orbitals of theheavy atom.
There are significant corrections to the rotation and spin-rotation interactions
that are worth addressing. Due to the precise nature of trying to measure an eEDM ina molecule, it is important to understand where tiny corrections can arise. A dominant
contribution comes from the centrifugal distortion of the end-over-end rotation of themolecule. Physically, this is related to the stretching of the bond as the molecule rotates
about its center of mass. In so doing, there will be corrections to the Hamiltonian
presented in Eq. 3.8.
H(b) = (Bν − Dν N2 )N2 + (γν − γDν N2 )N · S.

(3.10)

In general, any operator acting within the manifold of rotational states will have centrifugal distortions. The general distortion elements are obtained by successive ordersof N2 acting. In the above equation, this is performed once. The value of D ν is reduced
from Bν by a factor of the me /µmol , where µmol is the reduced mass of the molecule.
This is easily seen from a Dunham-type expansion [62]. While this expansion has theisotopic dependence thoroughly worked out for singlet states [63], the general featuresof the reduced mass scaling in general hold for doublet states. The expansion of thepotential for vibration and rotation terms isE(ν, J) ≈Xkl

lµ−(k+2l)/2 Ukl (ν + 1/2)k J(J + 1) − Λ2 ,(3.11)

49
where Λ = 0 for Σ molecules. The Ukl are isotopically invariant parameters of theinteraction potential. Terms with k = 0 have no vibrational dependence at this level oftheory. The term Dν is related to the Dunham parameter U 02 by a minus sign and scalesas (me /µmol )2 . Thus, for heavier molecules the distortion effects are small. γ Dν will scalein the same manner as Dν . Therefore, the higher order distortion terms will be quite
small. As an example, in YbF γν = −13.4 MHz, γDν = 4 kHz, and γHν = 25 Hz [64].
Each successive term in the series expansion reduces the interaction energy 2-3 ordersof magnitude.
The matrix elements of the rotational Hamiltonian in Eq. 3.10 are given as follows:h(N S)JMJ |H(b) |(N S)JMJ i = (Bν − Dν N (N + 1))N (N + 1) + (γν − γDν N (N + 1)) × S N J 
N +J+SΠ [S, N ] ,(3.12)(−1)

 N S 1 
where Π [S, N ] =p
S(S + 1)(2S + 1)N (N + 1)(2N + 1). This Hamiltonian is diagonalin S, J, and N . MJ is the projection of J onto the laboratory fixed axis. The deconstruction of the elements into the form above takes advantage of the Wigner-Eckhart
theorem. There are many standard references, of which the best are in Refs. [65, 66, 67].

In addition, many extremely useful examples are worked out in the book by Brown andCarrington [16].
The next energy scale to deal with in the spectroscopy is the hyperfine interactionsof the F-nucleus with the spin S and rotation N . In the case of the F-bearing moleculesin Table 2.4, all of the heavy atoms contain zero nuclear spin isotopes. Thus, theonly terms in the hyperfine Hamiltonian to consider are ones where the F nuclear spin
interacts with S and N .
HHFS = bF I · S −

µ 
√
0
10gS µB gN µN
T 1 (S, C2 ) · T 1 (I).
4π

(3.13)In the second term, the notation T 1 signifies a first rank tensor. The interaction is thefirst rank tensor formed from the coupling of S with the second rank reduced spherical50
harmonic C2 dotted into the first rank tensor of I. To be clear, the term T 1 (S, C2 ) is
given by

√ X
 1 2 1 Tq1 (S, C2 ) = − 3(−1)q Tq11 (S)Tq22 (C) .
q1 ,q2
q1 q2 −q(3.14)

In other words, it is the electron-nuclear spin-spin dipolar interaction. The first termin Eq. (3.13) is the Fermi contact interaction. b F depends on the amplitude of thewave-function at the F nucleus via
2
bF = gS µB gn µN µ0 |Ψη |2 ,3

(3.15)

where Ψν is the wave function for the ν th vibrational level. The matrix elements of thecontact interaction are0h((N S)JI)F MF |I · S|((N S)J 0 I)F MF i = (−1)2J +F +I+N +1+S Θ[J, J 0 ]Π [I, S] ×





 S J0 N  I J0 F (3.16) J S 1 
 J I 1 Θ[J, J 0 ] =p(2J + 1)(2J 0 + 1). The contact term preserves the values of F , N , and I

but couples in differing values of J. Therefore, it modifies the N = 1 level of the 2 Σstate by mixing in the two separate J values. The dipole coupling term can bring instates of differing Λ due to the C functions. However, concentrating on the Σ statealone, yields√

10gS µB gN µN h((N S)JI)F MF |T 1 (S, C2 ) · T 1 (I)|((N S)J 0 I)F MF i =√0− 30t(−1)J +F +I+N Π [I, S] θ[J, J 0 , N, N 0 ]×



0






J J 1 






0
 N 2 N0
 I J F 


0 2


N
N





 J I 1 


0
0
0




 S S 1 

(3.17),

where t is defined as

t = g S µB gN µN µ   3 cos2 (θ) − 1 
0

4π

r3

.
η

(3.18)

51
The parameters r and θ refer to distance of the electron from the F nucleus and theangle with respect to the molecular axis. η signifies that the expectation is taken for aparticular vibrational level. This interaction can couple in states of different N and J
while preserving S and I. Therefore, the ground rotational state N = 0 acquires a littleof the same parity state N = 2 with the differing value of J 0 = J + 1. J can only differ
from J 0 by one as can be seen via one the top row in the 9 − J symbol in Eq. 3.17.
In addition to these hyperfine effects, there is one other effect of interest. The
nuclear spin can interact with the end-over-end rotation of the molecule N. It takes theform of
HnRot = cF I · N(3.19)

cF is the strength of the interaction for the F nucleus. The elements of this interaction
are simple enough to work out. However, a quick glance at the form of c F will revealthat it is that the interaction is vastly smaller than the contact term. c F ∼ gr µB gN µN ,where gr is the rotational g factor and is reduced from g S by the ratio me /µmol ; therefore
it is 3 orders of magnitude smaller than the interactions in Eqs (3.16) and (3.17).
Lastly, these experiments will be performed in electric and magnetic fields. It istherefore useful to know how these molecules will react to an applied field. The Zeeman
interaction is dominated by the magnetic field manipulating the free electron. Another,smaller effect, comes from the magnetic moment of the molecular axis due to rotation.
The electron spin-Zeeman interaction is of the form
HZ = gS µB T 1 (B) · T 1 (S).

(3.20)The matrix elements in the coupled representation |((N S)JI)F M F i (N couples to S to

52
make J which in turn couples to I to make F )h((N S)JI)F MF |gS µB T 1 (B) · T 1 (S)|((N S)J 0 I)F 0 MF i

(3.21)

p
0= gS µB BZ (−1)F −MF +F +2J+I+N +S Π [S] (2J 0 + 1)(2J + 1)(2F 0 + 1)(2F + 1)








0
1 F  F J I  J S N 
 F
.
×


 J0 F 0 1  S J0 1 −MF 0 MF

The interaction does not preserve the value of F or J. Since B does not act on themolecular axis, N is unaffected. A simpler way to break this down would be to work inthe basis |N MN SMS IMI i since each individual spin interacts with the magnetic field.
This would require a different decomposition of the matrix elements in the hyperfine
interactions in Eqs.(3.16) and (3.17). However, in eEDM experiments it is usuallyrequisite to have a small magnetic field. This ensures that systematics in the experiment
do not contribute much error. Therefore, F is nearly a good quantum number and thecompletely coupled representation has its merits. A bonus that arises is that one canwrite down the effective magnetic g-factor in for a given F state.
√
gF = 6(−1)F +2J+N +1 Θ2 [F, J]Π [F ] F J I 
 J S N ×,
 J F 1 
 S J 1 

(3.22)(3.23)

where Θ2 [F, J] = (2F + 1)(2J + 1). This is how each level responds to a small appliedmagnetic field, small when compared to the hyperfine energy splitting.
There are two other magnetic interactions: nuclear moment and molecular rotation can each interact with the applied magnetic field. These interactions will be smaller
by the ratio of the nuclear to Bohr magneton, but important in precision measurements.
The rotational magnetic moment interacts with an applied field in the following manner
HZ,rot = −gr µB T 1 (N) · T 1 (B),

(3.24)

53
with matrix elementsh((N S)JI)F MF | − gr µB T 1 (N) · T 1 (B)|((N S)J 0 I)F 0 MF i=

(3.25)

0−gr µB BZ (−1)F −MF +F +2J+I+N +S Π [N ] Θ[J 0 , J, F 0 , F ]








0



1 F 
F J I
J N S  F× J0 F 0 1  N0 J0 1 −MF 0 MF.

The nuclear spin magnetic moment interacts with the magnetic field via
HZ,I = −gI µN T 1 (I) · T 1 (B),

(3.26)

h((N S)JI)F MF | − gI µN T 1 (I) · T 1 (B)|((N S)J 0 I)F 0 MF i

(3.27)

yielding elements of the form=

−gr µB BZ (−1)2F −MF +J+I+1 Π [I] Θ[F, F 0 ]




0

 F I J 
F
1
F


×



 I F0 1 −MF 0 MF.

The Stark effect is another matter. An electric field couples to the dipole momentof the molecule which is oriented along the molecular axis. Therefore, an electric field
will act on N . However, the electric field will need to be rotated into the frame of themolecule (or vice versa) and this will bring in a new degree of complexity. However, alittle patience and thought tells one that an interaction of the form
HS = −d · E,

(3.28)

where d is the molecular electric dipole moment, will produce matrix elements of theformh((N S)JI)F MF | − d · E|((N 0 S)J 0 I)F 0 MF i=00(3.29)−dE(−1)F −MF +F +J+J +I+N +S Θ[J 0 , J, F 0 , F, N 0 , N ]









0
0




J N S
F J I
1 F 
 N 1 N 
 F
×
 .




 N0 J0 1  J0 F 0 1 
0 0 0−MF 0 MF

54
It is the last 3 − J symbol that is of importance; unless N + 1 + N 0 is even, this vanishes.
Therefore, N 0 = N ± 1. The Stark effect only couples in states of differing N , or
opposite parity since the parity of a state is given by (−1) N . Thus, in order to polarize
the molecule, one must over come the splitting between adjacent N levels, or an energyof 2B(N + 1). An energy of this size requires a polarizing electric field of at least|Epolarize | & |2B|(N + 1).
d

(3.30)For the 2 Σ molecules in Table 2.4 this polarizing field ranges from a few to a few 10s
of kV/cm. In exchange, one gets an Eeff of many GV/cm, thereby an enhancement ofnearly 105 , far better than in the atomic case.
When one accounts for all the above, measurements on the transitions between
the various sub-levels can be accounted for in an accurate manner. For a 2 Σ molecule,one wants to measure the transition between a spin-up and a spin-down electron inparallel and anti-parallel electric and magnetic fields. Therefore, in a molecule like
YbF, one needs to measure the transition |F = 1, M F = 1i → |F = 1, MF = −1i. Thisis because the spin of the electron and the spin of the nucleus are coupled, even in thepresence of the strong electric field. A diagram is presented in Fig.3.6.
The magnetic fields serve to raise levels with M F > 0 while electric fields push
all MN levels down, thus all MF levels. In Fig. 3.6, the Stark shift is labeled by theblue lines. The red lines indicate the Zeeman shift, which only affects the |M F | = 1
lines at first order. An eEDM acts on the spin degree of freedom and therefore inparallel fields it enhances (the purple lines) the Zeeman shift while in anti-parallel (Ereversed from B) fields it diminishes (the green lines) the Zeeman effect. One looks
to measure the subtle frequency splitting between these two cases, as indicated by thetransition W . The difference between parallel fields and anti-parallel fields leads toan expression W k − W anti−k = 2de Eeff . However, small uncertainties in the ability toperfectly switch the alignment of the electric to magnetic fields will cause systematics.

55

W

ParallelAnti-Parallel

EZeem

F=1

EZeem

M=-1

EhyperN=0, J=12

EStark
M=0

F=0
M=+1

Figure 3.6: The basic hyperfine spectrum for the N = 0 rotational state of a 2 Σ molecule.
The Stark shift is denoted by the blue lines while the red lines mark the Zeeman shift.
In parallel (anti-parallel) fields the eEDM causes an energy shift labeled by the purple(green) lines. The transition labeled W and marked by an orange curve is of interest
in an eEDM experiment. The frequency difference in parallel and anti-parallel fields isdue to the eEDM.

56
Therefore, accurate magnetometers are requisite.
2 Σ molecules are a very basic system to consider for an eEDM study.

However,the fields required to polarize the molecules are still large. It takes several 10s of kV/cm
to align many of these molecules in an external field. While these fields are attainable ina lab, the systematic effects can scale unfavorably. Often, smaller fields are applied anda hit is taken in the effective electric field since the molecule is only partially aligned,
one gets some of the effective electric field due to averaging effects. Therefore, a look at
systems that are easier to polarize is a natural extension. However, these systems areoften composed of more than one valence electron. This causes a collection of electronic
surfaces with which the able practitioner of ab initio methods much contend.

3.3∆-type molecules
Many of the molecules presented in Table 2.4 are not of 2 Σ symmetry. One of thefirst molecules to stray from the 2 Σ doctrine was PbO in the metastable a(1) state [68].
This notation is already a bit different from the standard system. It refers to the firstexcited state of Ω = 1. Here, Ω is the projection of the sum of orbital and spin angularmomentum projections onto the molecular axis. In the case of PbO, only this sum isconserved. PbO in the a(1) excited state is an example of a Hund’s case (c) coupling
scheme. Fig. 3.7 gives a semi-classical illustration of this scheme.
The reason for the preservation of Ω has to do with the large value of the spinorbit interaction, which is large enough to overcome the electronic energy separation.
In the case of PbO, the 3 Σ1 and 3 Π1 states are coupled by the spin-orbit interaction
to form two Ω = 1 states. These states are in turn comprised of orbital configurations.
The 3 Σ1 state is primarily of a π1α π2α configuration (where α corresponds to a spin-up
electron along the internuclear axis), which would nominally be of zero help to an eEDM
search. However, there are admixtures of the σ 1α σ2α configuration when one allows forconfiguration interaction effects as described in the MCSCF and MRCI calculations in

57

J

L

Ja
S

Figure 3.7: The Hund’s case (c) coupling scheme vector diagram. The J and J a vectors
each have projection Ω onto the molecular axis. In this case L and S interact so strongly
with each other that they overcome the electronic energy separation.

58
Sec. 3.1. The latter configuration can be very useful in an eEDM search since there
are two electrons in distinct σ molecular orbitals. Because the electrons are in distinct
orbitals, each can contribute to the calculation of E eff .
The 3 Π1 state is composed of a π1α σ2α -type configuration. This configurationinteracts via spin-orbital effects with both of the 3 Σ1 configurations. The end result isthat individual electron spins and orbital angular momenta are inadequate to describe
the system. Only the total projection will suffice. The methods outlined in Chapter 2
are applicable so long as one accounts for the contributions from the 3 Σ1 and 3 Π1 states
individually and appropriately adds them together.
A chief advantage of the metastable PbO system is that it is far easier to polarize
than the 2 Σ system. A phenomenon known as Λ- or Ω-doubling allows the couplingof states of +|Ω| and −|Ω|, and in the absence of electric fields this coupling forces
two states to emerge: the symmetric and anti-symmetric combinations of | + |Ω|i and| − |Ω|i. Therefore, there is no net orientation of the molecule in the absence of an
applied field and therefore no permanent dipole moment. However, this interaction
produces an energy difference between states of opposite parity that is considerably lessthan the rotational splittings of 2 Σ molecules.
It is the metastable nature of PbO that makes it a tough candidate to workwith. It favors rapid decay to the ground state, a state with little to no favorable eEDM
characteristics. However, the push to move away from molecules of 2 Σ flavor had begun.
Quickly 2 Π molecules like HI+ [28, 40] and PbF [38] were proposed and re-studied fortheir applicability in eEDM searches. The former were found to be inefficient due totheir dominant π-molecular orbital characteristics. However, PbF exhibited strong case(c) type couplings and the mixing of the 2 Σ1/2 with the 2 Π1/2 leads to applicability inan eEDM search. Then a couple of rogue theorists proposed 3 ∆1 molecules for eEDM
searches [28]. It was found that the 3 ∆ molecules have very favorable Λ-doubling (aswill be discussed in Sec. 3.3.2 and arise chiefly from a σ α δ α configuration. In fact, the59
σ-orbital gives the science signal while the δ-orbital makes it easily polarizable. Now it
is time to learn more about these fascinating 3 ∆ creatures.

3.3.1

Structure
Unlike molecules of the fluoride and alkali-metal variety of the previous sections,3 ∆ molecules are a whole other beast. 3 ∆ molecules formed by one atomic d and one

atomic s orbital are of interest since they most easily lead to σ α δ α configurations. Sinced-electrons are of interest one is immediately led to consider transition row elements.
Because of large Z favoring, the 3rd row transition metals are ideal. It is here that
atoms with the proper characteristics are found. For the purposes of this section thediscussion will follow ThF+ because there is no published work on the molecule 2 aswell as HfF+ , because this is being pursued in house at JILA.
Th is a very heavy (Z = 90) element in the lanthanide row. Hf is also heavy(Z = 72). The thing these two atoms have in common is their atomic ground state,
which is comprised of 5d2 6s2 for Hf and a 6d2 7s2 for Th. By once ionizing and pairingwith an F atom, the possibility of an atomic configuration ds on Hf and Th arises, theother electron being whisked away by the ever electronegative F atom. However, there
are two other possibilities for the remaining electrons: they can occupy an s 2 or a d2
configuration. Neither of these is really amenable to an eEDM search without mixing ofconfigurations. Thus, it remains a job for ab initio methods to understand the electronic
properties.
When there are multiple electrons to consider, then one must use the information
given in the prior paragraph to approach the ab initio problem efficiently. Namely, theexpected atomic configurations are only valid in the region where F is close enough tocapture an electron from the heavy atom. Second, the remaining atomic orbitals canbe used to predict the dominant molecular orbital configurations. For instance, the2Therefore, this is new material with which to whet your knowledge appetite

60
s2 configuration will lead to a σ 2 molecular orbital and hence a 1 Σ electronic state.
However, the sd atomic configuration will lead to σδ, σπ, and σσ 0 configurations, which
in turn lead to electronic symmetries 1,3 Σ, 1,3 Π, and 1,3 ∆. σ 0 is the σ-molecular orbital
formed by the d electron. The d2 configuration will lead to a slew of possible states
ranging from symmetries similar to those given as well as 1 Γ and 1,3 Φ. As is evident,
this is many more states than was dealt with in the 2 Σ molecules. What remains tobe see is whether the 3 ∆, the one portended to be very useful for eEDM searches, is a
viable electronic state for the eEDM search.
In order to calculate the potential energy surfaces of the ThF + and HfF+ molecules
I employed the use the molpro suite of codes [45]. The RHF-MCSCF+SO-MRCI
method was used at various points in the internuclear separation to determine theground state [48, 49, 53, 54]. The RHF was performed starting at the atomic densities
and finding the wave function for the 1 Σ arising from the (sσ)2 configuration, where thes refers to the Th or Hf s atomic orbital as the dominant contribution to the molecularorbital σ.
After performing the RHF, the MCSCF was gradually built up to include the 1 Σ,
3 ∆, 1 ∆, 3 Π, 1 Π, 3 Σ+ , and the 3 Σ− . The last state arises from the (δ) 2 configuration. It

was determined that including the 1 Γ, 1 Φ, 3 Φ was necessary to converge the lower states.
The MRCI calculation was performed separately within each spin and space symmetrygroup, with the reference spaces of the other spatial symmetries present. This allowed
for convergence of ∆, Π, and Γ states which have degeneracies within two spatial groups.
This approach is to be contrasted with the previous work on HfF + [41]. In that paper
only the states arising from the σ 2 and σδ configurations were studied. The inclusionof the 3 Σ− state affects the other Ω = 1 levels arising from the 1,3 Π1 states because the3 Σ− exists in the same energy range as the 1,3 Π .
1In order to account for spin-orbit effects, I employed the fully relativistic effective
core potentials (ECP) and triple zeta basis sets of the Stuttgart group for Hf [69] and the

61quasi-relativistic (scalar terms only) ECP and segmented basis set for Th [70, 71, 72].
These account for the relativistic effects associated with spin-orbit coupling. It separates
out the various Ω sub-levels of a symmetry, e.g. 3 ∆ → 3 ∆1 , 3 ∆2 , and 3 ∆3 . From thispoint in the calculation the best determination of the appropriate Hund’s case can bemade.
To account for the polarizability of the atoms I included in the active space thenext-lying atomic p-orbital, i.e. 6p for Hf. After each MRCI calculation a spin-orbit(SO) calculation was performed that included all the calculated states and provided
mixing amongst the levels with the same value of Ω. The results of the potential energy
surface (PES) calculation are presented in Fig. 3.8. As is clearly seen in the figure, theground state is difficult to declare because it lies within the uncertainty (a few hundredcm−1 is a conservative estimate) of the ab initio methods. However, given comparison
to the known ThO (isoelectronic to ThF + ) electronic levels and a similar calculation’s
ability3 to reproduce the lifetime of the metastable 3 ∆1 state, there is confidence incalling the 1 Σ0 state the ground electronic state.
The admixture of various other Ω = 1 values into the 3 ∆1 state is rather minimal.
It is found that most (≥ 95%) is due to the 3 ∆1 and therefore Hund’s case (a) quantum
numbers are appropriate for describing these 3 ∆ systems.
Since it is expected that the ground state may turn out to be the 1 Σ0 in both
HfF+ and ThF+ , it is instructive to estimate the lifetime of the excited 3 ∆1 state.
Nominally, this state would never decay because it needs to change Λ by two units and
S by one unit. However, Λ and S are not preserved under the influence of spin-orbit
effects. Thus, the admixture of 1 Π1 into the 3 ∆1 allows for spontaneous emission from
3∆

1 →

1Σ .
0

I find about a 2% admixture of the 1 Π1 in both HfF+ and ThF+ . Using

the energy difference between the minima of the respective curves, I obtain a lifetime
3

I performed the same calculation at the known bond length of ThO in the 1 Σ state and used thetransition moments calculated from the 3 ∆1 state to find the lifetime. I obtained a few ms, and recently
the ACME collaboration has measured the lifetime to be ∼ 1.8 ms [73]

62

HaL

-10 000

E Hcm-1 L-20 000-30 000-40 000-50 000
1.5

1.6

1.7

1.8

1.9

2.0

2.1

E Hcm-1 L-30 000

1

S0

3

D1

3

D2

3

D3

3

P 0+

3

P1

3

P2

1

P1

1

D2

3

S0+

3

S1

3

P 0-

2.2

HbL

-35 000

1

S0

3

D1

3

D2

3

-40 000

P0+

3

P1

3

P2

1

P1

1

D2
S0+

3

-45 000

3
3
3

1.8

1.9

2.0
2.1
R HÞL

2.2

2.3

D3

3

S1
P0S0-

Figure 3.8: Results of the many state calculation on HfF + (a) and ThF+ (b) at the
RHF-MCSCF+MRCI+SO level of theory.

63
on the order of seconds for these two molecules, more than enough time to make ameasurement in an ion trap.

3.3.2

Spectroscopy
Given the analysis of the 3 ∆ states in Sec. 3.3.1, it is apparent that the electronic

state is separated well enough in energy from electronic states with the same value of Ω
to be described by a set of Hund’s case (a) quantum numbers. These numbers are thetotal angular momentum sans hyperfine J, the total electronic spin S, the projectionsof orbital and spin angular momentum onto the molecular axis Λ and Σ, the sum ofΛ + Σ = Ω, and in the presence of fields the projection of J onto the axis defined by
the field MJ . We will return to the case of hyperfine interactions later in this section.
Fig. 3.9 gives a visual of the vector diagram describing Hund’s case (a).
While L is drawn in the figure, the value of L is ill-defined due to the lack ofspherical symmetry. In some cases, having a defined L is a good approximation, but
it must be noted that it is merely that, an approximation. Much of the spectroscopy I
will discuss is built from the idea of approximation as a way to guide intuition. Alongthese lines, various contributions to the spectroscopic Hamiltonian used in analyzing ∆molecules will be discussed.
The first, and most important, is the new energy scale introduced by the non-zerovalue of L and S. The interaction of L with S induces a splitting between states ofdifferent Ω. In the HfF+ molecule, the splitting between Ω = 1 and Ω = 2 is 1200 cm −1 .
The splitting between Ω = 2 and Ω = 3 is 1900 cm −1 . The reason behind the asymmetry
will be dealt with shortly. The main idea to take away is the energy scale. States within
the same electronic symmetry are separated by about thousand or so cm −1 . Contrast
and compare this with the rotational energy splittings of 2 Σ molecules of 0.1–10 cm−1 .
This new energy scale will be important in understanding the nature of parity splittings.
The simplest way to construct the interaction is to only consider the diagonal

64

J

L

S

L

S
W

Figure 3.9: The Hund’s case (a) coupling scheme vector diagram. The J and L + S
vectors each have projection Ω onto the molecular axis. In this case L and S interact
with the molecular axis as well as with each other.

65
contribution to the interaction due to the non-sphericity of a diatomic molecule. On
the diagonal the contribution from spin-orbit is
HSO = AΛΣ +2λ(3Σ2 − S2 ),3(3.31)

where A is the spin-orbit constant and λ is the electronic spin-dipolar interaction. From
the ab initio calculation A is about 790 cm −1 . Since Hf is much heavier than F, thespin-orbit contribution to the molecular case is dominated by the contribution from the
Hf atom. Assuming that the orbital angular momentum l of the d electron from Hf is agood quantum number, then the Van Vleck approximation [61] can be used to calculate
the molecular spin-orbit constant.
Using wave functions in terms of Hund’s case (a) quantum numbers (labeled by|Λ; S, Σ; J, Ωi with J ≥ Ω), the energy separation in the molecule can be compared tothe atomic system. In terms of Slater determinants, the molecular wave functions are:|3 ∆3 i = |2; 1, 1; J, 3i(3.32)= |dδ α sσ α ||3 ∆2 i = |2; 1, 0; J, 2i=(3.33)

1√ (|dδ α sσ β | + |dδ β sσ α |)2

|3 ∆1 i = |2; 1, −1; J, 1i(3.34)= |dδ β sσ β |.
The spin-orbit energy shift for the 3 ∆3 is thenh3 ∆3 |ALz Sz |3 ∆3 i = 2A

(3.35)

h|dδ α sσ α ||a(l1z sz1 + l2z sz2 )||dδ α sσ α i = a(2(1/2) + 0(1/2))= a.
Now apply the total spin lowering operator (given by S − =(3.36)
P−i si ) to Eq. (3.32) toobtain the 3 ∆2 state. Since the projection of Σ is zero, there is no shift. Therefore,

66
the molecular spin-orbital constant A is half the atomic spin-orbit constant a, seen bycomparing Eq. (3.35) with Eq. (3.36). In Hf, this method would predict a molecularspin-orbit constant of Aexpec = 610 cm−1 (obtained via the spectroscopic informationin the Moore tables on Hf+ for the d-electron [74]), which is not too far from the abinitio value.
The discrepancy in the energy difference between the three Ω levels has to deal
with the fact that the individual electron spin-orbit interaction will couple Slater determinants with 1 ∆2 and 3 ∆2 , thereby creating an interaction between the spins; theeffect of λ. The singlet state is given by|1 ∆2 i = |2; 1, 0; J, 2i=(3.37)

1√ (|dδ α sσ β | − |dδ β sσ α |).
2

The interaction of the atomic spin-orbit constant between the singlet and triplet configurations leads to the estimation of λ. Were the electronic energy separation comparable
to the atomic spin-orbit constant, then Hund’s case (c) would apply. Since the 1 ∆2state is over 8000 cm−1 away an estimate of the magnitude by which the singlet statepushes down the triplet state via second order perturbation theory can be made. Thus
the 3 ∆2 is expected to be pushed down by the 1 ∆2 an amount 260 cm−1 whereas the abinitio calculation shows it deviates from the expected value by about 360 cm −1 . Thus,|λ| ≈ 250 cm−1 .
For a 3 ∆ molecule, there are quite a few terms in the spectroscopic Hamiltonian.
A simple basis is preferred even though the interactions are not necessarily simple. The
idea of an effective Hamiltonian, which was used for 2 Σ molecules earlier, is extremely
useful in this case. Firstly, one only wished to include terms which act in the manifoldof 2S+1 ∆Ω states, i.e. interactions that account for the vast array of possible effects but
only serve to act within the 2S+1 ∆Ω parameter space. Therefore, these interactions maychange the value of Ω, connect −|Λ| to +|Λ|, and change the value of J, but they will

67
only do so in such a way as can be described in the basis set |Λ; JΩ, SΣi.
The end-over-end rotation of the molecule is described by
HRot = B(J − S)2 + γ(J − S) · S,

(3.38)In Eq. (3.38) the terms (J − S) are the equivalent of N in the 2 Σ case. In case (a), N
is not a good quantum number. In fact, states with N differing by unity (but with thesame value of J − S) can be very close in energy. These are related to the phenomenonof Λ-doubling.
Λ-doubling arises from the Coriolis coupling due to the end-over-end rotationof the molecule. States with differing values of L are mixed. Recall the form of thespin-rotation operator in Eq. (3.9). Now consider a Π state and couple in an excitedΣ state through the perturbative expansion in (3.9). The interaction returning to theΠ state can connect to a state with the same value of Λ = +1 (which gives the spinrotation parameter for the Π state), or can connect to the Π state with Λ = −1. In thelatter case a term which couples states of +|Λ| to those with −|Λ| arises. Therefore,
in the absence of an applied electric field, the ground states will be symmetric andantisymmetric combinations of ±|Λ|.
In a ∆ state, Λ-doubling cannot happen at second order in perturbation theory
because a Σ state with Λ = 0 cannot be coupled in. Therefore, in a perturbative
treatment, one will need 4th -order perturbation theory. The mixing caused by thisapproach will depend on the energy separation of the ∆ state from both Π and Σ
states.
Recall from Fig. 3.8 that the approximate separation of the electronic states ofinterest is known. The general process to find the number of parameters is to take anexpansion of the sum of HRot and HSO raised to the 2|Λ| power. To do so, there willneed to be 2|Λ| − 1 energy denominators. In what follows, the first line is a schematic

68
and the second line is the result after simplifications (see Refs. [16, 75] for more details)
HΛD ∝ (HRot + HSpin )2|Λ| /(∆E)2|Λ|−1
HΛD =

1
1
1
4
4
3
3
2 2
2 2
q̃∆ (J++ J−) − p̃∆ (J+S+ + J −S− ) + õ∆ (J+S+ + J −S− ) − (3.39)
2
2
2
1
1
3
3
4
4
m̃∆ (J+ S++ J − S−) + ñ∆ (S+
+ S−
).
2
2

The last two terms on the bottom line of Eq. (3.39) are irrelevant for 3 ∆ molecules because they flip the spin projection Σ beyond the maximal/minimal values and therefore
annihilate the state. Each operator is such that (∆Ω + ∆Σ) − ∆Λ = 0. For example,
the õ∆ is an operator which takes Ω = 1 → Ω = −1. For the 3 ∆1 states of interest
for an eEDM search, this is the operator which causes a direct splitting between thesymmetric and antisymmetric combinations of ±|Λ| states. The operators p̃ ∆ and q̃∆connect states with ∆Ω = ±3 and ±4 and therefore affect the 3 ∆1 state via higher
orders in perturbation theory.
Expressions for õ∆ , p̃∆ , and q̃∆ are given by [75]





S S 2  (2S − 2)!
√VA VA VB VBõ∆ = 4 30
∆E1 ∆E2 ∆E3 
 1 1 S0 
 (2S + 3)!
√
VA VB VB VBp̃∆ = 4 35
∆E1 ∆E2 ∆E3VB VB VB VBq̃∆ = 8,∆E1 ∆E2 ∆E3(3.40)(3.41)(3.42)

where VA(B) is the matrix element of the spin-orbit (rotational) Hamiltonian between
differing states. h3 ∆1 |AL− |3 Π1 i is an example of VA , whereas h3 ∆1 |BL− |3 Π0 i is an
example of VB . The ∆Ei are the energy differences between the state of interest andthe intermediate states. For a 3 ∆ state built from s and d atomic orbitals, the numberof Π and Σ states is limited to a few. The sum is fairly straightforward to calculate. In
HfF+ , the Ω = 1 state is of concern, and it is governed by the õ ∆ parameter. Edoub is69thus (recall that J = 1 in the ground state)
Ω=1
Edoub
= 2õ∆ J(J + 1)√
8
2 2
6×5! 30A B
J(J + 1)2d≈(E3 ∆ − E3 Π )2 (E3 ∆ − E1 Σ )(3.43)= 2 × 10−7 cm−1 .

Using methods similar to the polarizing field in Eq. (3.30), one can write
Epolarize &

Ω=1
Edoub
,
dmol

(3.44)

which leads to an Epolarize ≈ 50 mV/cm. The value of dmol = 4 Debye obtained via themolpro calculations is used. In HfF + the splitting between states of opposite parity inthe ground J = 1 level is ωef = 4õ∆ = 10 kHz. It should be noted that this is including
the 1 Σ state which is actually dominated by the atomic s 2 configuration. Thus, theestimate includes a reduction which arises from the mixing of d 0 contributions into thes2 state, which is accounted for by the presence of  d in Eq. (3.43). There are two powersof d because it appears twice in the summation; once for each appearance of 1 Σ.

3.3.3

Hyperfine interactions in 3 ∆1 molecules
Because Fluorides are present again, there will be hyperfine structure. Being a bit

more complicated because of the orbital motion, there are three terms, two of which aresimilar to 2 Σ molecules given in Eq. (3.13). Because there is orbital angular momentum,
a new term ∝ I · L is present.
~ + b~I · ~S + cIz Sz .
HHFS = ℵ~I · L(3.45)The term with ℵ is the orbital angular momentum interacting with the nuclear spin. I’ve
included a simplified form of the contact and spin-dipolar interactions from Eq. (3.13).
Due to the expected strong Hund’s case (a) nature of these molecules, spectroscopic
measurements will not identify individual parameters in the above equation, instead

70
only finding the net energy shift
h. . . |HHFS | . . . i = (ℵΛ + (b + c)Σ)Ω = hΩ .

(3.46)| . . . i signifies a state with the relevant quantum numbers of interest. Note that changingΩ → −Ω implies Σ → −Σ and Λ → −Λ therefore leaving this expression invariant, as itshould be in order to be time-reversal invariant. In the limit of pure case (a), there areno Ω changing operators. However, given enough measured transitions, it is possible toassign values to ℵ, b, and c in the hyperfine Hamiltonian. For clarity, the relation ofb to bF is given by bF = b + (1/3)c. bF absorbs part of the spin-dipolar coupling into
it’s definition. It is a little easier to deal with in the 3 ∆ molecules. In addition, thespin-dipolar term has been greatly simplified with many of the constants being lumped
into c.
~ in Eq. (3.45), one may ask
Because there exists a term proportional to ~I · L
whether it can contribute to terms similar to the Λ-doubling Hamiltonian; the answer isyes. In order to see the origin of the exact terms an expansion is needed. Note that thehyperfine interaction is smaller than the spin and rotation interactions since it is reduced
by a factor proportional to µN /µB , the ratio of the nuclear to Bohr magneton. Thus,a perturbative approach can be taken akin to the method used to find the Λ-doublingterms. Once again, 4th -order perturbation theory is required to connect Λ = ±2 toΛ = ∓2. Thus
HP.E. ∝ ((HRot + HSpin ) + HHFS )2|Λ| ,(3.47)

where P.E. refers to perturbative expansion and terms that involve the first power of2
HHFS are kept. Because terms proportional to H HFS
are going to be even smaller, they

are ignored. The first term in the expansion of Eq. (3.47) is just the usual Λ-doubling
Hamiltonian as in Eq. (3.39), so it has already been worked out. The next term is
HHFSΛD ∝ 2|Λ|HHFS (HRot + HSpin )2|Λ|−1 /(∆E)2|Λ|−1 /(∆E)2|Λ|−1 .

(3.48)

71
In spectroscopic terms this yields an expression of the form
HHFSΛD =

1
1
3
3
2
2
c∆ (J+
I+ + J −I− ) − d∆ (J+I+ S+ + J −I− S− ) +
2
2
1
1
2
2
3
3
e∆ (J+ I+ S++ J − I− S−) − f∆ (I+ S++ I − S−).
2
2

(3.49)

Here the notation I+ and I− is used to indicate the raising and lowering operators of I
that act on the internuclear axis. Therefore, I + and I− raise and lower the value of Ω
because I couples to J.
Of the four terms in (3.49), only the d ∆ term has been previously published, in astudy of the NiH molecule where there is a curiously large Λ-doubling for a ∆ electronic
state [76, 77]. From what is known, the remaining three terms are new. The simple
explanation for the algebra that leads to the expression in (3.49) is that since I ± acts on
the internuclear axis projection, one merely is swapping instances of the interaction BL ±with ℵL± , or replacing one instance of the rotational Hamiltonian with the hyperfine
orbital Hamiltonian. Therefore, the term e ∆ can be written as a perturbative sum ina manner similar to õ∆ in Eq. (3.40). Note that there are many ways in which topermute this interaction, three times more than ways in which one can permute theregular Λ-doubling interaction.
Using this, the expectation for the size of the hyperfine Λ-doubling parameters
can be expressed in terms of their regular Λ-doubling counterparts. The four terms c ∆ ,d∆ , e∆ , and f∆ can be related to the terms q̃∆ , p̃∆ , õ∆ , and m̃∆ . Thus
ℵ
q̃∆ ,
B
3ℵ
≈ −
p̃∆ ,
2B
ℵ
≈ − õ∆ ,
B
1ℵ
≈ −
m̃∆ .
2B

c∆ ≈ −2(3.50)

d∆(3.51)e∆f∆(3.52)(3.53)The minus sign is due to the replacement of −2BL ± with ℵL± . There is no term
proportional to ñ∆ because this parameter contains only terms which raise and lower

72
on Σ. Now, since ℵ is not an easily determinable parameter in a pure Hund’s case (a)molecule, either many measurements are needed, or this scaling relation is to be treatedas very approximate. If one can measure the term h Ω (c.f. Eq (3.46)) for both 3 ∆1 and
3 ∆ , the average will yield a value of ℵ. In addition, measuring h in the 3 ∆ state will
3
2
2

give the value of ℵ as well since Σ = 0 in that state. Therefore ℵ = h 2 /2 = (h1 + h3 )/4.
The ability of the terms in Eqs. (3.50)–(3.53) to predict the size of the interaction canbe seen in NiH. There, (h3/2 + h5/2 )/4 = 22.8 MHz and p̃∆ = 188.6 MHz. This would
yield a prediction for d∆ = −0.03 MHz. The measured value is d∆ = 0.8(1) MHz. As isevident, this estimate is off by more than an order of magnitude and has the wrong sign.
The discrepancy is hard to locate since the experimental work is not entirely positive
about the assignment of d∆ . However, NiH is a rather complicated molecule in thesense that there are many d electrons to account for. This complicates the perturbative
calculations. In HfF+ , there is only one d electron and this simplifies the number ofelectronic states to consider. Thus, the scaling rule developed in Eqs. (3.50)–(3.53) is
expected to be a better predictor.
3∆

3.3.4
3∆

1 molecules in electric and magnetic fields

1 molecules are interesting. Because N is no longer a good quantum number,the electric and magnetic fields will both act on J, the sum of N and S. I will separate
the electric and magnetic interactions in what follows.

3.3.4.1

Electric fields

I now turn to the calculation of the application of electric and magnetic fields.
First, I will address the Stark effect. As in the case of 2 Σ molecules, the Stark effectacts along the internuclear axis. However, N is not a good quantum number. Thus, theelectric field acts on J. The form of the interaction is the same as in Eq. (3.28). The

73
matrix elements are
0hηJΩIF MF | − d · E|ηJ 0 Ω0 IF 0 MF i = −dE(−1)F −MF +F +2J+1+I−Ω Θ[J, J 0 , F, F 0 ] ×



0
0
J
1
J
F
1
F



 (3.54)−Ω 0 Ω−MF 0 MF



0
0

 J F I ,×
 F J 1 

where Θ[J, J 0 , F, F 0 ] is the same as in Eq. (3.16). This interaction preserves
the value of0 J 1 J 
Ω and MF . In fact, this would seem to imply a linear Stark shift since ∝−Ω 0 ΩΩ when J = J 0 . However, in the presence of the interactions in Eq. (3.39), the groundstate is given by linear combinations of +|Ω| and −|Ω|. Thus, the Stark effect is zero
to first order in E because the two terms cancel. However, should one be in a field large
enough to overcome the splitting caused by the parameter in Eq. (3.40), the term responsible for splitting levels of symmetric and anti-symmetric combinations of ±|Ω|, thenthe linear Stark regime enters. The field must be larger than that given by Eq. (3.44).
The intent is two work with fully polarized molecules, thus the best choice of basis isthe Ω basis.
The way in which to define whether the regime of a signed Ω, i.e. linear Stark
shifts, is by whether or not the inequality|dE|

J(J + 1) + F (F + 1) − I(I + 1)
 |õ∆ |J(J + 1),
2F (F + 1)J(J + 1)

(3.55)

holds. Given the numbers for d and õ ∆ in HfF+ , the requisite field needs to be |E| 
50 mV/cm, same as the result in Eq. (3.44); the polarizing field. Thus, fields on theorder of several V/cm will suffice for polarizing the molecule and choosing the signedΩ basis. Luckily, these fields can be efficiently constructed in the lab in contrast to
the fields required to polarize 2 Σ molecules. In addition, the Stark shift illustrates thatstates with the same MF Ω go the same way in energy. Thus, unlike Fig. 3.6, there will

74
be an upper and lower component. This is due to the Λ-doubling and provides a way
to check systematics by measuring shifts in the upper component and compare them toshifts in the lower component. This will be discussed a little later after we understandthe Zeeman interactions.

3.3.4.2

Zeeman interaction

Next is the Zeeman interaction. Unlike the Stark effect, the Zeeman terms are
horrendous. The magnetic field will act on anything that has a magnetic moment,
hence the electron spin, the electron orbital angular momentum, the rotational angularmomentum, the nuclear spin, and then even higher order corrections. You guessed it, I
will go through each in a simple manner and estimate the size of the effect. The basic
Zeeman Hamiltonian is given by 4 terms:
HZeem = (gL + gr )µB B · L + (gS + gr )µB B · S(3.56)−gr µB B · J − gN µN B · I.
The spin and orbital pieces combine to givehκ|HZeem (S, L)|κ0 i = ((gL + gr )Λ + (gS + gr )Σ)µB B ×
0(−1)F −MF +F +2J+I+1−Ω Θ[F, F 0 , J, J 0 ] ×




0
0
1 F   J 1 J   J0 F 0
 F




 F J
−MF 0 MF−Ω 0 ΩX  J 1 J0   S 1+(gS + gr )µB B


q=±1
−Ω q Ω−Σ q0

×(−1)F −MF +F +2J+I+1−Ω+S−Σ Θ[F, F 0 , J, J 0 ]Π[S]





0
0
0

J F I 
1 F 
 F
.
×





F J 1
−MF 0 MF

(3.57)


I 


1 

S 

Σ0

The use of κ is to signify the quantum numbers of interest. They are the same as thequantum numbers in the Stark effect in Eq. (3.54). I have separated out the contribu-

75
tions that preserve the value of Ω and those that change it. Notice that those whichchange the value of Ω also change the value of Σ. This is to keep zero change in Λ.
This term is usually labeled the anisotropic spin-Zeeman effect. It is responsible fordecoupling the electron spin from the molecular axis as the strength of the magnetic
field is increased. It is often easiest to denote the interaction via g l multiplied by theΩ-changing operators.
The nuclear and rotational Zeeman terms arehκ| − gN µN B · I|κ0 i = −gN µN B(−1)F −MF +J+I+1+F Θ[F, F 0 ]Π[I]





0
0

1 F 
F I 1  F× I F J 
−MF 0 MF0hκ| − gr µB B · J|κ0 i = −gr µB B(−1)F −MF +J+I+1+F Θ[F, F 0 ]Π[J]





0
0
0

1 F 
F J 1  F× J F I 
−MF 0 MF

(3.58)(3.59)

These Zeeman interactions are the dominant ones. Their size is easy to estimate. For
the spin and orbital pieces collect terms to find that g L Λ + gS Σ ≈ 0. This is because
gL Λ = 1 and gS Σ = −2 in the 3 ∆1 . Small perturbations originating from QED effects
as well as interactions with excited electronic states will cause g L to differ from 1 andgS to differ from 2. While QED is hard to discern, the electronic effects scale fromthe inclusion of excited states with the same value of Ω into the state of interest, i.e.
3 ∆ . The inclusion of spin-orbit coupling will bring in 1,3 Π states into the Ω = 1 wave
1
1

function. The Zeeman matrix element h 3 Π1 |HZeem |3 ∆1 i 6= 0. Therefore, the cross terms
arising from taking the hΩ = 1|HZeem |Ω = 1i matrix element (which is a combination of
1,3 Π

1 and

3∆

1 states) will not be zero. The size of this effect will scale as A/∆E, where

A is the spin-orbit constant and ∆E is the electronic energy separation. From the abinitio calculations, this is a 0.1–1% effect depending on the state coupled in. Thus, thesum gL Λ + gS Σ ≈ 0.1 at the largest.
This is one of the appealing features of a 3 ∆1 state, it is relatively immune to76small variations in an applied magnetic field. The dominant contributions nearly cancel
each other out. The remaining terms are g N and gr , both of which are of the order andme /µmol . Therefore, these interactions are of the order 10 −3 and thus also quite small.
The anisotropic g-factor gl , which accounts for the mixing in of other Ω states and helps
to decouple the electron spin from the molecular axis, is also of order 10 −3 . Because it
works to decouple spin, it can be related to the other spin-decoupling interactions, likespin-rotation. In fact, to make an estimate, swap one instance of BL ± in the expression
for γ in Eq. (3.9) with the magnetic field. In so doing, it is seen that g l ≈ γ/B, where
B is the rotation constant. In OH, where extremely detailed spectroscopy has been
performed, gl = γ/B = 6 × 10−3 , while the measured value is gl = 4 × 10−3 [16]. Thisis excellent agreement for such a simple argument.
The remaining Zeeman terms are all related to the orbital Zeeman interaction
and involve higher orders. As in the case of the Λ-doubling and hyperfine induced Λdoubling, the orbital Zeeman interaction will cause Λ-doubling to occur. Interactions
which connect +|Λ| → −|Λ| will be Λ-doubling related. However, there will also be terms
that connect Λ → Λ and thus will not be parity dependent. Brown and coworkers [77, 16]
have written down the effective Zeeman Hamiltonian. It is arrived at by taking the sumof the HSpin + HRot and B · L to the 2|Λ| power and dividing by the energy differences,as was done in Eq. (3.47). The result is
other
HZeem
=

−
+
−
−

(3.60)µB 0µB
grD (B+ J− J+ J− + B− J+ J− J+ ) +g (B+ J+ J+ J+ + B− J− J− J− )
2
2 rD
µB
µB 0
glD (B+ S− J+ J− + B− S+ J− J+ ) −g (B+ S+ J+ J+ + B− S− J− J− )
2
2 lD
µB
µB 0
grS (B+ S− S+ J− + B− S+ S− J+ ) +g (B+ S+ S+ J+ + B− S− S− J− )
2
2 rS
µB
µB 0
glS (B+ S− S+ S− + B− S+ S− S+ ) −g (B+ S+ S+ S+ + B− S− S− S− )22 lS

In the above I have collected the terms that are similar. Primes denote Λ-doublingterms. The first line describes the coupling of the rotation of the molecule with the

77magnetic field. This is very much akin to centrifugal distortion effects and is thuslabeled with a rD for distortion due to rotation. The second line is akin to a distortionof the anisotropic correction (think g l ). Thus, they are labeled with an lD. The B ±signify the raising and lowering of angular momentum along the internuclear axis, thus
are Ω changing. Each interaction changes Ω. Terms with an same number of B ± andJ∓ operators will return Ω to the same initial value; g rD and glD .
The final two lines are higher-order spin interactions and are thus labeled withrS for spin-spin-type corrections to the rotation and lS for spin-spin-type corrections
to the anisotropic terms. The last line is anisotropic because the final Ω state must be
different from the initial one.
Provided that the electronic states that are coupled in are limited to configurations arising from the sd-atomic configuration, then the magnitude of the higher-orderg-factors are expected to be the same in the primed and unprimed interactions. This isbecause they are limited to talking with excited Π and Σ states only. However, if one
has Φ and Γ states, then the primed and unprimed g-factors will differ from each otherin magnitude.
Assuming that the primed and unprimed terms will be of similar size because
they talk with the same electronically excited states, the size of the g-factors can be
estimated in a manner similar to the c ∆ etc. terms:
q̃∆
B
3 p̃∆
≈ −
2 B
õ∆
≈ −
B
1 m̃∆
≈ −
2 B

0
grD
≈ −2

(3.61)

0glD(3.62)

0
grS
0
glS

(3.63)(3.64)

0 term that is of interest. It connects states of Ω = pm1 →For the 3 ∆1 state, it is the grSΩ = ∓1 and therefore acts differently on the states of opposite parity in the absence ofthe electric field. õ∆ = 10 kHz was estimated, which yields this term to be of the order

78
0 = 10−6 .
grS

This is important since it changes the way in which states with even (odd) parity
respond to the application of a magnetic field, thus causing a systematic shift thatmimics an eEDM signal in an eEDM measurement. However, in the absence of theelectric field this term is of order 2 × 10 −6 . In the presence of the electric field strong
enough to polarize the molecule, where Ω is a signed quantity, this interaction is offdiagonal and therefore only contributes in second order and thus is negligible. The scale
0 µ B)2 /2dwill be (grSB
mol E, or the strength of the Λ-doubling Zeeman shift to the Stark

splitting between states of opposite Ω (but same M F ).
However, there is an important effect to consider. The electric field couples in
excited rotational states of the molecule. Thus, there could be an electric field dependent
difference in the way the molecules respond to an applied magnetic field. See Fig. 3.10
for a physical picture. As is evident in the figure, the lines with J 0 = J + 1 and M Ω < 0(> 0) are gained upon (gaining on) the lines of J with M Ω < 0 (> 0). This causes
the states with M Ω < 0 to have a stronger coupling to the magnetic field as a functionof applied electric field than their M Ω > 0 counterparts. This can be seen from a
perturbative approach˜ M Ω > 0i = |J, M Ω > 0i + η> |J + 1, M Ω > 0i,|J,(3.65)

˜ M Ω < 0i = |J, M Ω < 0i + η< |J + 1, M Ω < 0i,|J,(3.66)whereη≷ =hJM Ω ≷ 0|HStark |J + 1, M Ω ≷ 0i.
2B(J + 1) ∓ γF M ΩdE(3.67)J(J + 1) + F (F + 1) − I(I + 1),
2F (F + 1)J(J + 1)

(3.68)

The factor γF is given byγF =the diagonal contribution to the Stark interaction. It is like an electric g-factor. Now
apply the Zeeman Hamiltonian to the the states | J˜i ( hJ˜|HZeem |J˜i). Taking the appro-

79

5

J=2

E Hunits of BL

4
3
2

MW=-1

1

J=1

0

MW=0

-1

MW=+1
0.0

0.5

1.0
2.0
1.5
dipole ´ Electric Field Hunits of BL

2.5

Figure 3.10: The Stark effect in 3 ∆ molecules that shows how the application of anelectric field can change the way in which the molecule responds to an applied magnetic
field in different Ω states. The axes are in units of the rotational constant B. Whenthe energy of the field is comparable to B, we enter a new regime of the Stark shift as
it deviates from linear. The Λ-doubling constant has the exaggerated value B/100 so
as to be somewhat visible. This distorts the range over which the linear Stark effect isapplicable. The dashed lines in the upper part of the panel correlate to the solid linesof the same color in the lower portion of the panel. The black and red arrows indicate
the coupling of M Ω states.

80
priate matrix elements by applying Eqs. (3.57) and (3.54) to the terms and expanding
the denominators in Eqs. (3.65) and (3.66) to the first order in dE/B yields
δgF (E) =gF
dEΠ[F, F 0 , J, J 0 ]B(J + 1) γF Ω
0
0
J ,F
2 
2 


0
0
1 F   J 1 J   F0
 F
×

 


−J
−Ω 0 Ω−MF 0 MFX

(3.69)
J0
F

2

I 

.


1 

In the level of interest (J = 1, M Ω = ±1) for eEDM spectroscopy the difference between
positive and negative M Ω is
δgF =3/2
9 dE=.
gF =3/2
40 B(3.70)

This is about a part in 105 .
The two transitions of interest are labeled in Fig. 3.11. The upper transition W uwill have a slightly different shift in frequency than the lower one W ` due to the eEDM.
A systematic that must be controlled is the difference in magnetic response due to theelectric field dependent g-factor difference. What is nice here is that there is no needto reverse the sign of the magnetic field relative to the electric field because the 3 ∆1
molecules have a built in co-magnetometer; the Λ-doublet. However, whereas in the 2 Σcase the sensitivity was limited to the ability to exactly reverse the applied magnetic
field, here the sensitivity is to the difference in magnetic response. The difference
W u − W ` ∝ de Eeff + δgF µB B.
The blue lines indicate the Stark shift while the red lines indicate the Zeeman
shift. The õ∆ has been greatly exaggerated. The eEDM shift is denoted by the green
lines. One way in which to cancel out the effect of the varying g-factors is to chopthe magnetic field. This is discussed in the forthcoming paper from the JILA eEDM
collaboration [78]. In so doing, the difference in the transitions W u and W ` is
W u (B) + W u (−B) + W ` (B) + W ` (−B) = 8de Eeff +

δgF
µB B,
gF

(3.71)

81

Wu

EZeem
EStark
4oD

Wl

Figure 3.11: The basic Stark (blue lines )and Zeeman (red lines) spectrum of a 3 ∆1
molecule. The transition labeled W u is of interest in an eEDM experiment. The “comagnetometer” transition labeled W ` is also of interest as the difference between W u
and W ` will cancel out the magnetic field shifts provided the g-factors are the same inthe upper and lower components of the Λ-doublet. The Λ-doublet splitting has been
greatly exaggerated as well as the eEDM shift labeled by the green lines. Black lines
indicate the zero field shifts.

82
which is 4 times stronger than the 2 Σ case with the added benefit of having a weakerdependence on the systematic control of B due to the smaller g-factors.

Chapter 4

Beyond the Geometric Phase

The mathematical difficulties of a theory of rotation arise chiefly from a want ofgeometrical illustrations and sensible images, by which we might fix the results of theanalysis in our minds.
– James Clerk Maxwell
And so begins over 25 years of research into the geometric phase introduced by
Berry in 1984 [18]. In the proposed experiment by the JILA eEDM team, the molecularions will be in a rotating electric field [78]. This electric field will couple to the electric
dipole moment of the molecule and in so doing introduce an additional phase into the
dynamic evolution of the internal states of the molecule. It is this additional phase,
which will appear as an energy shift in the measurement, which must be understood.
The ions will rotate in the plane defined by θ r = π/2 (the angle the electric field makeswith the axis of rotation), which gives the maximum coupling between states of M
differing by unity (as will be seen in the following discussion).
In addition, the ions will be confined in the z-direction by an electric field thatwill change the value of the θr = π/2 small amounts and the plane of rotation is shifted
up and down. While this effect will be ignored in the development of the dressed state
picture, it will be included in the final section (4.6) as a discussion of how it may affecta measurement in the 3 ∆1 system. I will develop a formalism whose punchline is that,while it complicates a measurement of the eEDM, does not prohibit such a search. This

84
formalism takes many steps, and some simple examples will be worked out so as to build
intuition.

4.1

The basics
Any quantum mechanical system in a stationary state accumulates a dynamicalphase over time proportional to the energy of that state. To determine energy differences, based on phase differences accumulated between two such states, is the basis ofRamsey spectroscopy; the workhorse of high-precision measurement. For this reason,
small effects that can add spurious phase shifts must be understood and kept undercontrol. What effects, you may ask? Effects like the ones which crop up when a particle
is driven by a periodically rotating field, which creates non-stationary states.
If the total Hamiltonian H(t) has an explicit time dependence, then this dependence will generate an additional phase evolution. For example, precision spectroscopyof trapped ions must contend with the fact that the ions are in motion, and experience
varying ambient fields during the course of their orbit. Otherwise, these ions would leave
the trap, thereby making an electron electric dipole moment (eEDM) search irrelevant.
In the case of a Hamiltonian with a slow, periodic time dependence H(t + τ ) =H(t), Berry [18] has given a famous description of the additional phase. Berry’s original
treatment requires that the period τ be far larger than any other relevant time scale ofthe system, and thus finds an “adiabatic” phase shift. This shift is largely independentof the detailed way in which the Hamiltonian varies with time, and leads to an elegant
geometric description of the phase [18, 79, 80, 81, 82, 83, 84]. Maxwell would be so
proud for finding such a description.
Extensions to this formalism have considered the next-order corrections if therate of change of the Hamiltonian is not strictly adiabatic [85, 86, 87, 88, 89, 90, 91].
A more general Floquet theory has also been advanced, which allows one to consider
the effect of overtones of the fundamental period τ [92, 93, 91]. In addition, the ideas

85
have been extended to particles with dynamic properties [94], gauge structure [95],the quantum Hall effect [96], to relativistic effects using the Dirac equation [97], and tosupersymmetric black holes in 5 dimensions [98]. Yes, I said supersymmetric black holes
in 5 dimensions thereby bringing us full circle to supersymmetry from the introduction.
This will be the last mention of supersymmetric black holes in 5 dimensions.
Thus far, applications of the Berry phase have mostly considered the effect of thetime-dependence on quantum mechanical particles without internal structure, althoughatoms with two or several levels have been considered [99, 93, 100]. However, thejob of precision spectroscopy is precisely to reveal this internal structure. Corrections
to Berry’s phase arising from degrees of freedom internal to an atom or molecule isour concern in understanding the intricacies of a trapped molecular ion in an eEDM
experiment. To establish a concrete formalism for this, we will consider a particularcase, namely, a diamagnetic or electrically polar species in the presence of a magnetic
or electric field, whose direction precesses on a cone with an angular frequency ω r (seeFig. 4.1). The system evolves in time according to the field variation, combined withwhatever intrinsic Hamiltonian governs the particle’s internal structure. The internal
structure dictates regimes of linear and quadratic Zeeman (Stark) shifts with respect tothe applied magnetic (electric) field.
A main point in deriving the non-dynamic phase in this situation is to recognize
the periodicity of the driving field. By analogy to the periodic driving of a near-resonant
laser field applied to a two-level atom, we consider “field-dressed” states of the Hamiltonian in the spirit of quantum optics [101, 100]. This viewpoint effectively counts theenergy of the atom itself, plus that of the photons of frequency ω r arising from thedriving field. The additional energy shift due to the rotating field is then equivalent tothe ac Stark effect in optics. By constructing the complete Hamiltonian in this way, we
are able to accommodate the particle’s internal structure. We are also able to consider
arbitrary rates of rotation, not just those that are adiabatic with respect to the parti-

86

Figure 4.1: The axis of rotation with laboratory-fixed coordinates {ξ, η, ζ} as well as
the field coordinates defined by {x, y, z}. The field direction rotates about the ζ-axis
with angular frequency ωr .

87
cle’s Hamiltonian. Nevertheless, in what follows we will focus primarily on results for
low rotation rates, to better draw analogies with the usual adiabatic phase [18]I will walk through the basic derivation of the dressed state formalism in Sec. 4.2
and find the general transformation from a Hamiltonian with an explicit time-rotating
field, into an effective dressed Hamiltonian whose eigen-energies yield the shifted energies. I’ll illustrate this transformation first with a simple two-level atom, then generalize
it to an arbitrary atom or molecule. In Sec. 4.3 I’ll briefly re-visit a structureless particle
with arbitrary total spin, showing that the results reduce to Berry’s in the limit of slow
rotation. Sec. 4.4 illustrates the application of the method to a particle composed of
two interacting spin-1/2 objects, to show most clearly the effect of their fine structureon the Berry phase. Sec. 4.5 considers a simple case of a dipolar molecule in a rotating
electric field, to assess the influence of molecular end-over-end rotation on the phase.
After having understood these basics, I’ll address the form of 3 ∆1 molecules in a rotating electric field and a complexity that arises due to the Λ-doubling and rotation of theelectric field (Sec. 4.6).

4.2

General spin-j system: A dressed state derivation
A general derivation for the spin-j system will entail the use of a dressed state~
ansatz. A dipole µ~ interacting with a time-varying field F(t)can be described by thefollowing Hamiltonian~
H(t) = H0 − µ~ · F(t),(4.1)~ (t) can be electric or magnetic that acts on an appropriate moment µ
where F~ of the~ rotates on a cone at frequency ωr and tilt angle θr as depicted in
atom or molecule. F
Fig. 4.1. Here H0 is a Hamiltonian in the absence of the applied rotating field. It canbe used to describe the hyperfine elements of an atom or it can be a detailed molecular
Hamiltonian that includes such items as rotation, spin-spin, nuclear spin, or λ-doubling.

88
The Hamiltonian can equally be represented in a basis referred to the axis of rotation or
to the instantaneous field axis. Later I will take the instantaneous field axis. I’ll begin
by quantizing along the axis of rotation. Place this structured object in a rotating field~ let there be an electric or magnetic dipole that interacts with the field in the usualF;way, i.e. it is a scalar interaction of two vectors.
To work with this Hamiltonian, it is convenient to pick two basis sets:|(κ)jmζ i|(κ)jmj i(4.2)

Because j is the total of all relevant angular momenta, its projection onto an axis isunambiguously defined as mζ in the lab fame and mj in the rotating frame, as above.
Here κ is a shorthand notation for all the other quantum numbers required to specify
the state.
To deal with the explicit time dependence of the field rotation, I will expand into
the lab basis first, and will a trial wave function motivated by dressed states with alittle ingenuity in the choice of phase;|ψ(t)i =Xκ0 ,j 0 ,m0ζ0Cκ0 ,j 0 ,m0ζ e−imζ ωr t |(κ0 )j 0 m0ζ i.

(4.3)

We have explicitly included a time dependent phase factor with phase m ζ ωr . Taking
the time derivative for the time-dependent Schrödinger equation (TDSE) and projecting
onto a particular state, gives
h(κ)jmζ |i

d|ψi 
= iĊκ,j,mζ + mζ ωr Cκ,j,mζ e−imζ ωr t .
dt

(4.4)

As for the internal Hamiltonian H0 , it may or may not be diagonal in this basis, but it
does not depend on any external field. Therefore it can be represented in a basis where
it is diagonal in mζ , wherebyh(κ)jmζ |H0 |ψi =Xκ0 ,j 0 ,m0ζ0ei(mζ −mζ )ωr t h(κ)jmζ |H0 |(κ0 )j 0 m0ζ iCκ0 ,j 0 ,m0ζ δmζ ,m0ζ

(4.5)

89
To treat the field interaction, I’ll use the language of tensor algebra, and express~ in the lab frame as an explicit rotation from F~ in thethe spherical components of F~
rotating frame (whose z axis is, of course, defined by the instantaneous direction of F
itself):
X

Fι =

ι

1?
Fq Dιq(ωr t, θr , 0)1?
= FDιq(ωr t, θr , 0).

(4.6)

F is the magnitude of the field, and q is its spherical projection in the rotating frame.
~ defines this frame so only the values of q = 0 will contribute. D is a Wigner
But F
rotation matrix. In a similar manner, the dipole moment µ~ is determined by its sphericalcomponents such that~−~µ · F

X

= −

ι

= −F

= −F

(−1)ι µι F−ι

X
ι

X
ι

1∗
(ωr t, θr , 0)(−1)ι µι D−ι0µι e−iιωr t d1−ι0 (θr ).

(4.7)

This uses the explicit expression for D in terms of a little-d function [102].
Just as I treated the internal degrees of freedom in H 0 I must now treat the fieldinteraction.
~ |ψi = −Fh(κ)jmζ | − µ~ ·FXκ0 j 0 m0ζ ι(−1)ι h(κ)jmζ |µι |(κ0 )j 0 m0ζ i ×
0Cκ0 ,j 0 ,m0ζ d1−ι0 (θr )eiωr t(−ι−mζ ) .

(4.8)

Piecing together the different parts, and multiplying through by e imζ ωr t , a new TDSE
is arrived at for the coefficients C:
iĊκ,j,mζ + ωr mζ Cκ,j,mζ=X

κ0 ,j 0Fh(κ)jmζ |H0 |(κ0 )j 0 mζ iCκ0 ,j 0 ,mζ −X

κ0 j 0 m0ζ ι(−1)ι h(κ)jmζ |µι |(κ0 )j 0 m0ζ iCκ0 ,j 0 ,m0ζ ×0

d1−ι0 (θr )eiωr t(−ι−mζ +mζ ) .

(4.9)

90
~ is, nor which structural degrees of freedomNow, nowhere is specified what the field F
are involved in making the dipole µ~ , and it does not matter. All that matters is that µ~ isa vector, in which case the Wigner-Eckhart theorem applies [102]. In the total angularmomentum basis, it must beh(ν)jmζ |µι |(ν 0 )j 0 m0ζ i ∝ 

j
−mζ

1

j0

ι

m0ζ




,

(4.10)

where the proportionality constant involves the reduced matrix element. Then the conservation of angular momentum implies that m 0ζ − mζ = −ι. However, this immediately
removes the time-dependence in the exponential term in (4.9). In fact, this statement
says that any angular momentum imparted by the rotating field must be accounted forin the projection mζ .
In some cases it will prove more useful to keep track of the individual spin components mζi separately. For instance, suppose there were two angular momenta, m ζ1
and mζ2 : we would have two projection terms that would each evolve as e i mζ1 ωr t andei mζ2 ωr t . Terms in the Hamiltonian which describe the interaction of the two spins areof the form ~s1 · ~s2 for which the interaction scales as





s1
−mζ1

hs1 mζ1 s2 mζ2 |~s1 · ~s2 |s01 m0ζ1 s02 m0ζ2 i ∝1s02  i (m −m0 )ω t i (m −m0 )ω t
1 s01   s2
 e ζ1 ζ1 r e ζ2 ζ2 r . (4.11)00−mζ2 −p mζ2
p mζ1

The proportionality involves a reduced matrix element. By the conservation of angularmomentum it is noted that mζ1 − m0ζ1 = −(mζ2 − m0ζ2 ) and the phase factor is stillcanceled out. In fact, for any such interaction between two spins, the conservation ofangular momentum forces the time dependence to cancel out.
With the time-dependence removed, Eq. (4.9) reduces to the Schrödinger equation
for a non-rotating field tilted at an angle θ r from the rotation axis. This introduces anadditional term on the left of (4.9), which is moved to the RHS and interpreted as an

91
effective Hamiltonian. Thus if H0 is presented in the basis |(κ)j mj i diagonal withrespect to the field, then the matrix to be diagonalized is~ − ω r mζ
Hdressed = H0 − µ~ ·F~ − ω r jζ ,= H0 − µ~ ·F(4.12)

where mζ is the eigenvalue of the jζ operator. Now rotate this Hamiltonian from the m ζbasis to the mj basis. Since H0 does not depend on the either mζ or mj , it is unaffectedby this rotation. In the frame of the instantaneous field, where m j is the good quantum
number, the dressed Hamiltonian is written as~ − ω̂r · ~j,Hdressed = H0 − µ~ ·F~ − ωr (cos(θr )jz − sin(θr )jx ).
= H0 − µ~ ·F(4.13)

Here is the key result. All the time-dependence is removed. This Hamiltonian has beenpreviously formulated in NMR studies [103]. In the following sections I will apply it toa few elementary cases of interest.

4.3

Pure spin-s system
As the simplest application of the general method beyond the spin-j particle, I

consider in this section a structureless particle of arbitrary spin s, as was consideredin the original formulation of Berry [18]. This spin interacts with a magnetic fieldthat rotates at an angle θr with respect to the axis of rotation. Using the result from
Eq. (4.13), this system is described by the Hamiltonian
Hdressed = ωL sz − ωr (cos(θr )sz − sin(θr )sx ),(4.14)

where ωL = gs µB B is the m-independent Larmor precession frequency and g s is theg-factor for the spin-s. For this section, I have reverted to the usual notation s and m
for the spin and it’s projection onto the instantaneous field axis.

92
For this structureless particle, the Hamiltonian (4.14) is represented by a (2s + 1)
× (2s + 1) tridiagonal matrix, in the basis of states |s mi. This matrix is explicitly givenby

b(s, m)
0
0
...
 ma



..


 b(s, m) (m − 1) ab(s, m − 1)
0
.




.
.

..
..
H=
0
b(s, m − 1)b(s, −m + 1) 
,




..


.
0
b(s,
−m
+
1)
−(m
−
1)
a
b(s,
−m)




...
0
0
b(s, −m)−m a.
where a = ωL − ωr cos(θr ) and b(s, m) = (1/2)

p(4.15)

s(s + 1) − m(m − 1) ωr sin(θr ). Ap-

pendix B sketches a derivation of the eigenvalues of this matrix, which are
λm = mq
ωL2 + ωr2 − 2ωr ωL cos(θr ),(4.16)

where m takes on the values −s, . . . , +s in integer steps.
The usual Berry phase is obtained in the adiabatic limit where ω r  ωL , in whichcase
λm ≈ mωL − mωr cos(θr ).

(4.17)The magnetic field completes one rotation in a time τ = 2π/ω r . In this time the spin
accumulates a dynamical phase ϕm = mωL τ . Beyond this, it acquires an additional
phase γm = φm − ϕm , where φm = λm τ , given to lowest order by(0)γm= −m2π cos(θr ) ⇒ 2πm(1 − cos(θr )).

(4.18)In the final step, the fact that adding 2πm (where m is either integer or half-integer)
amounts to adding a phase of ±1 to the system is used. Since Ramsey-type measurements are the main concern, i.e. knowledge of phase differences between two sub-levels,
this added phase is unobservable. However, in interferometric measurements, half integer spins will introduce a sign change in the state which is observable. However, this a93additional phase contributes an apparent extra energy of 2π∆M to a Ramsey-type measurement, which is always an integer multiple of 2π and hence, unobservable. The phase(0)γm accumulated is exactly that given by the result of Berry; m times the solid angle
subtended by the rotation. This solution can be extended to regimes of non-adiabaticity.
The first order correction in ωr /ωL is(1)γm= 2π mωr
sin2 (θr ),2ωL(4.19)

which has already been identified elsewhere [85, 91]. Based on our explicit formula, we
can extract corrections to any desired order, at least for fields undergoing the simple
motion in Fig. 4.1. This additional phase can be expanded to any desired order in the
adiabatic parameter ωr /ωL . For example, the second and third-order γ (k) corrections
are
(2)
= 2πm
γm

ωr2
cos(θr ) sin2 (θr )2ωL2(4.20)

(3)
γm
= 2πm

ωr3
(3 + 5 cos(2θr )) sin2 (θr )16ωL3(4.21)

Using the general dressed formalism, the limit of fast field rotation can also be
described. The phase γm (after one field period) can be approximated in this limit(ωr  ωL ):γm ≈ 2πm − 2πmωLcos(θr ),ωr(4.22)and the first term is unobservable. In this case the dominant energy, as manifested in thephase, is the photon energy due to the time-periodic field. On top of this, the magnetic
field interaction itself makes a small correction. This is clearly not the appropriate limit
in which to perform precision spectroscopy, since small uncertainties in the field rotation
rate would dominate the observable Larmor frequency.
A spectroscopic measurement would involve finding the energy difference between two states with different values of m, with difference ∆m. In a Ramsey-type

94
experiment, this measurement seeks to measure the phase difference ω L ∆mτ = ∆ϕ.
In a rotating field, however, the experiment will produce a measurement of ∆φ =q∆m ωL2 + ωr2 − 2ωL ωr cos(θr )τ , and thus will introduce an error. This error is givenby the difference ∆γ = γm − γm0 = ∆φ − ∆ϕ, and is plotted in Fig. 4.2 as a function ofrotation rate. The different curves represent different values of the tilt angle θ r .

4.4

Structured spin-J system
More generally, atoms and molecules are composite objects made of individual

spins, which are moreover coupled together to create fine or hyperfine structure. For
example, alkali atoms couple the electronic and nuclear spins into a total hyperfine state.
The resulting angular momentum structure will have a bearing on the non-adiabatic
corrections to the geometric phase accumulated. Ref. [104] has studied the effects of~ ·S~ coupling while Ref. [105] analyzed the Breit-Rabi
an atomic spin-J system with L
Hamiltonian assessing the influence of hyperfine structure on the Berry phase. Bothcoupling schemes can be easily addressed with the method illustrated below.
As a simple illustration of the formalism, consider a composite particle composedof two spin-1/2 objects. This example goes beyond the structureless particle often
envisioned by the usual Berry theory. The dressed Hamiltonian is given by
Hdressed = ω1 j1z + ω2 j2z + ∆~j1 · ~j2 − ωr (cos(θr )Jz − sin(θr )Jx ),(4.23)

where ωi = gi µB B is the Larmor precession frequency of spin j i ; J~ is the vector sumof ~j1 and ~j2 ; and ∆ is parameter that governs the splitting between levels J = 0 and
J = 1.
The Hamiltonian (4.23) can be represented by a 4 × 4 matrix, in the basis

95

Figure 4.2: The extra phase accumulated due to the rotation of the field. In thelimit of very fast rotation, ωr  ωL , the system accumulates a phase of 4π, whichis unobservable. In this limit, the states are best represented by projections onto theaxis of rotation. The various lines represent values of θ r between π/2 (bottom line) and
0 (top line) in steps of π/10. As can be seen, when θ r is zero, there is no measurable
phase shift, since there is no enclosed solid angle.

96
{|(j1 j2 )J MJ i} = |( 21 12 )0 0i , |( 21 12 )1 1i, |( 21 12 )1 0i, |( 21 21 )1 − 1i


− 3∆
4




0

Hdressed =  1 (ω1 − ω2 )
 2

0



1
2 (ω1 − ω2 )0∆
4 + ωZ − ωr cos(θr )ωr√sin(θr )20ωr√sin(θr )
2

∆
4

ωr
√
sin(θr )20ωr√sin(θr )2∆
4 − ωZ + ωr cos(θr )

0





,





(4.24)

where ωZ = 12 (ω1 + ω2 ), is the average of the individual Larmor frequencies. The first
item to note is that if the two spins have identical Larmor frequencies, ω 1 = ω2 , thenthis Hamiltonian is equivalent to that of a spin-0 particle and a spin-1 particle that are
independent of each other, there is no coupling between the two states. Each would
then evolve according to the previous section on pure spins. This would be the case forthe singlet and triplet excited states of the helium atom, (1s2s) 1,3 S state, for example.
However, should these spins be different from one another (such that ω 1 6= ω2 ) thencoupling corrections arise.
The ordinary adiabaticity criterion specifies that the rotational frequency ω r be
small as compared to the Larmor precession frequency ω L , which in this example isgiven by ωZ . However, now it becomes also necessary to specify whether the Larmor
frequency itself is large or small compared to the splitting ∆ between adjacent J-levels.
This is because the Berry phase arises from a correction to the eigenvalues of the dressed
Hamiltonian relative to the non-rotating Hamiltonian. It is therefore worthwhile to cast
the non-rotating Hamiltonian in the basis in which it is as diagonal as possible. In thefollowing sections we treat the two limits separately. Since our emphasis here is on the
Berry-phase limit, I consider only the limit where ω r  ωZ , where the rotation rate of
the field is small compared to the Larmor frequency. The resulting phase shifts are ofcourse implicit in the theory, however.

97
4.4.1

Weak magnetic field, ωr  ωZ  ∆In the low-field limit, but assuming that each Larmor frequency ω i is still far

larger than the rotational frequency ω r , one can write down expressions for the energy
quite simply. Note that in the absence of rotation, the leading-order energy shift is thesum of the Larmor frequencies themselves, i.e., (1/2)(ω 1 + ω2 )MJ = ωZ MJ . Leaving
this correction on the diagonal to break the degeneracy of the J = 1 level, one now
treats as perturbations the difference (1/2)(ω 1 − ω2 ) and the rotation rate ωr .
Doing so, the leading-order correction due to rotation of the field is given by the
diagonal terms in (4.24) that contain the rotation rate ω r . This correction is the usual
Berry phase found above,
γ (0) (|J MJ i) = −2πMJ cos θr ,(4.25)and it depends on the atomic state only through the total projection of angular momentum MJ . Thus the ordinary Berry phase in the limit of zero rotation rate is stillintact, and is independent of the internal structure.
However, the higher order corrections do depend on this structure. To leading
order in the rotation frequency ωr , a correction to the Berry phase in the |( 12 12 )1 1i
state is given by:
γ

(1)



(ω1 − ω2 )2ωr
2
sin (θr ) 1 +(|11i) = 2π.
2ωZ4ωZ (∆ + ωZ )(4.26)

The first term is the usual first order correction for a structureless particle (cf. (4.19)),with the replacement of ωL by ωZ . This should be expected since the energy splitting
between the two states is given by ωZ , and thus is what must be overcome by therotating field that couples together the differing projections. The second term in theparentheses depends on how strongly the rotating field couples states with differing
total J, as manifested by ω1 − ω2 . This new correction arises from 4th -order mixing in
perturbation theory, it is nevertheless linear in the adiabaticity parameter ω r /ωZ . A

98similar expression is found for the |1 − 1i state,
γ

(1)



ωr
(ω1 − ω2 )22(|1 − 1i) = −2πsin (θr ) 1 −.
2ωZ
4ωZ (∆ − ωZ )(4.27)

As is expected from the pure spin case, this state picks up an overall negative sign.
However, due to slight changes introduced by the structure, we find a slightly different
correction to the second term in parentheses. In fact, one can write down an expressionthat encapsulates the first order (in ω r /ωZ ) correction as
γ

(1)



ωr
(ω1 − ω2 )22.
(|J MJ i) = 2πMJ
sin (θr ) 1 + MJ
2ωZ
4ωZ (∆ + MJ ωZ )(4.28)

While the first term is exactly of the form in (4.19), the second term describes how the(1)

distant |J = 0, MJ = 0i state affects the accumulated first order phase γ MJ ; namelythat the quadratic Zeeman shift in the two M J = 0 levels distorts the system such thatthe |J = 1, MJ = 1(−1)i state is affected more (less) by the |J = 1, M J = 0i state.
The two states with MJ = 0 do not acquire a geometric phase at lowest orderin ωr , which is appropriate. In this case the leading order perturbation to the dressed(±)

Hamiltonian is EZ= ±[(1/2)(ω1 − ω2 )]2 /∆, which denotes the quadratic Zeeman shift

already present in the non-rotating system, and which does not contribute to the Berryphase γ. The quadratic shift after a period τ = 2π/ω r is the dynamical phase the
MJ = 0 would nominally acquire. To the first order in ω r in which there is a correction
to the |J = 0, MJ = 0i state arises in 4th -order perturbation theory. It is given by
(−)

γ

(1)

2EZ
ωr
sin2 (θr ) (|0 0i) = 2π
2  ,
2∆∆ 1 − ωZ

(4.29)∆

where as always the superscript “1” denotes a correction linear in ω r . Here we find aterm that appears similar to the MJ = 1 states, with the exception that it occurs in an
MJ = 0 state. A new energy scale has been introduced into the problem by adding ∆and this allows the |0 0i state to acquire a first order Berry phase. However, the strengthof this phase is reduced by a term proportional to the ratio of the quadratic Zeeman

99
shift in the lower level to the spin-spin energy splitting. Given our assumptions, thisterm — while linear in ωr — is a product of multiple small parameters, and is generally
smaller than γ (0) for MJ = ±1 states.
For the case of the |J = 1, MJ = 0i state, there is also a 4th -order correction, but
it takes a very different form. After much algebra,
(+)

γ

(1)

2E
ωr
(|1 0i) = −2π
sin2 (θr ) Z .
2ωZ
ωZ(4.30)

This is very different from the |0 0i state correction in (4.29). The important energy
scale is the linear Zeeman shift ωZ . Eqs. (4.29) and (4.30) carry an important insight;
the energy scale responsible for higher-order Berry phases is different for the two M J =0 states. The dominant scale in the |0 0i is the spin-spin splitting ∆. In the |1 0i,
the dominant energy scale is the linear Zeeman shift. To first order in ω r , there isa correction to the MJ = 0 states that, while similar to the shift in the |M J | = 1
states, is reduced in magnitude. This reduction is due to the structure, the structurethat provides a quadratic Zeeman shift in the M J = 0 states. For the lower (upper)
level, the correction depends on the relative strength of the quadratic Zeeman shift
to the spin-spin splitting (linear Zeeman shift). In the regime considered, both ofthese contributions are very small. The same ideas apply to the F = 0 and F = 1
hyperfine states of Hydrogen, where the magnetic field is coupling states of the same
parity. Briefly, γ (1) is influenced by “nearby” MJ = ±1 states for the |1 0i level, andcomparatively less influenced by the “far away” M J = ±1 levels in the |0 0i state.
It is instructive to examine these results for different cases of individual Larmor
frequencies. In the case where both particles experience the same Larmor frequency
in a field, ω1 = ω2 , then these first-order corrections reduce to the usual first-ordercorrections for a structureless spin-1 particle, as in Eqn. (4.19), and the additional
MJ = 0 pieces are zero as well. In another limit where one Larmor frequency dominates
the other, say ω1  ω2 , then γ (1) for the |MJ | = 1 states reduce to the first order100
correction of the dominant spin alone, reflecting the fact that the weaker spin is coupled
to the stronger one and gets dragged along for the ride. This happens, for example, in
the F = 1 hyperfine ground state of the hydrogen atom, where the nuclear g-factor is
far smaller than the electron g-factor.

4.4.2

Strong magnetic field, ω1 , ω2  ∆  ωrIn the other limit, where the magnetic field is large compared to the splitting

between adjacent J-levels, it is more useful to construct the dressed Hamiltonian in analternative basis. Namely, the non-rotating Hamiltonian is more nearly diagonal in the
independent-spin basis |j1 m1 j2 m2 i, where the four Zeeman energies Em1,m2 are given
simply by m1 ω1 + m2 ω2 :
E1,1
2 2

E 1 ,− 12

2

E− 1 ,− 122

E− 1 , 1
2 2

1(ω1 + ω2 )21=
(ω1 − ω2 )2
1
= − (ω1 + ω2 )2
1
= − (ω1 − ω2 ),2=(4.31)

as appropriate to this Paschen-Back limit of the Zeeman effect. This is an example of theaside in Sec. 4.2 where the ansatz (α, β) e −i m1 ωr t e−i m2 ωr t was made. The remaining
Hamiltonian, which includes the rotation of the field and the spin-spin interaction, is
recast as follows
ωr∆
2 sin(θr ) E 21 , 21 + 4 − ωr cos(θr )ωr
E 1 ,− 1 − ∆
2 sin(θr )422Hdressed = ωr02 sin(θr )−∆− ω2r sin(θr )2− ω2r sin(θr ) 


ωr
∆
sin(θ
)
−

r
2
2


ωr
∆
E− 1 ,− 1 + 4 + ωr cos(θr ) − 2 sin(θr ) 22− ω2r sin(θr )E− 1 , 1 − ∆
4
0

2 2

(4.32)

101
Once again, one immediately reads the Berry-phase contribution from the diagonalcomponents, as
γ (0) (|j1 m1 j2 m2 i) = −2π(m1 + m2 ) cos(θr )= −2πMJ cos(θr ).

(4.33)The phase accumulates due to the individual spins separately, as expected when thespins interact weakly with each other compared to their interaction with the field.
This independent accumulation of phase leads to a different interpretation of
the MJ = 0 states: in the limit of small magnetic field compared to the spin-spinenergy splitting, we had attributed this to an M J = 0 projection while here, we canattribute this to m1 = ± 12 accumulating ±(ωr /2) cos(θr ) extra energy and the m2 =∓ 12 accumulating ∓(ωr /2) cos(θr ). To cement this idea even further, there are two
independent first-order contributions to the first-order non-adiabatic correction γ (1) ,computed first neglecting ∆:γ (1) (|j1 m1 j2 m2 i) = 2π m1
(1)

ωr
ωr
sin2 (θr ) + 2π m2
sin2 (θr )
2ω1
2ω2
(1)

= γ1 (|j1 m1 i) + γ2 (|j2 m2 i).

(4.34)(4.35)

This is exactly the contribution one would expect from two independent spins following
a rotating field. When the spins are anti-aligned, or m 1 = −m2 , no correction exists at
this order. It is worth noting that this perturbative expansion breaks down if ω r ∼ ωi .
Thus, should the rotation rate be fast with respect to one of the Larmor frequencies,
but not the other, then the measured phase difference cannot be treated perturbatively
in this regime.
The explicit effect of internal structure, manifested in the splitting ∆, appears as

102
a next-order correction:
(1)
γ1

ωr
sin2 (θr ) 1 +→ 2π m1
2ω1



∆
2ω2

2 !

(1)
γ2

ωr
→ 2π m2
sin2 (θr ) 1 +
2ω2



∆
2ω1

2 !

(4.36).

(4.37)

Of course, there are many routes by which 4 th -order perturbation theory can affect thisstate. Only the one route which produces a phase shift proportional to ω r after one
period of oscillation is given. There is a structure correction for each non-adiabatic
spin that depends on the relative strength of the spin-spin splitting to the other Larmor
frequency. Thus, it is evident that the spin-spin splitting need be small compared toeach of the Larmor frequencies in order to make this expansion. Again, this is a more
restrictive condition on adiabaticity than is usually employed for two independent spins.

4.5

Polar molecules in a rotating electric field
Molecules bring yet another degree of freedom to the picture, namely end-over-end rotation with eigenstates |N MN i. In addition, if the molecule is polar, it has
an electric dipole moment that can be acted upon by a rotating electric field. In thissection I’ll consider only diatomic molecules, and only one of a fairly simple structure, toillustrate how the formalism applies to them. The lowest-order Berry phase was workedout recently in this system [100], but the higher-order corrections are implicit there aswell.
For the sake of illustration why not choose the simplest of diatomic molecules,
a 1 Σ molecule with no hyperfine structure. In a rotating electric field this system is
described by a Hamiltonian of the form
~2−µHdressed = B N~ m · E~ − ωr (cos(θr )Nz − sin(θr )Nx ),(4.38)~ is the end-over-end rotational angular momentum of the molecule, µ m is thewhere N
electric dipole moment of the molecule and E is the electric field strength. Working in

103
the frame of the electric field along with the electric dipole moment pointing along themolecular axis, there are no couplings of M N or Λ, where Λ is the projection of total
angular momentum onto the internuclear axis. For Σ-molecules, this means there areno couplings to excited electronic states by the applied electric field at the low fields
considered.
For simplicity, only the coupling only between the N = 0 and N = 1 rotational
levels of the molecule is considered, which assumes weak coupling of rotational states
due to the electric field, i.e., µm E  B. The formalism can of course be extended toarbitrarily large N values as needed. It is nice to note that this formalism has an atomic
analog: the 1 S0 and 1 P1 states of noble gas and alkaline-earth atoms have opposite-parity
and are coupled by the Stark interaction. This approach gives the corrections for statesof opposite parity coupled by the Stark interaction. The dressed Hamiltonian reads, inthe basis {|N MN i} = {|00i, |1 − 1i, |10i, |1 + 1i}√1 µm E
0
0
−
0


3




1
√
0
2B
−
ω
cos(θ
)
ω
sin(θ
)
0


r
r
r
2 r

 (4.39)
Hdressed = 11 − √1 µm E√ ωr sin(θr )√ ωr sin(θr )
2B


3
2
2


√1 ωr sin(θr ) 2B + ωr cos(θr )002Note the the electric Hamiltonian is off-diagonal in the basis of parity eigen-states. In theabsence of the perturbation ωr , this Hamiltonian appears to have a complete degeneracy
among the three states with N = 1. In the magnetic field case above, this degeneracy
was broken by the linear Zeeman effect acting on the diagonal matrix elements. To
achieve the same feat here, one must account for the off-diagonal mixing due to electricfield. Note the similarity of this procedure to that of Vutha and DeMille [100].
First diagonalize the MN = 0 subspace, using the mixing angle δ defined by
µm E
= −x,
tan(δ) = − √3B(4.40)

with the usual eigenvectors (cos(δ/2), sin(δ/2)) and (− sin(δ/2), cos(δ/2)). The explicit

104
values in terms of the parameter x ares√ δ
1 + x2 + 1
√
cos
=
2
2 1 + x2s√
 
1 + x2 − 1
δ
√
.
=
sin
2
2 1 + x2

(4.41)(4.42)In terms of this mixing angle the transformed Hamiltonian, with electric-field-dependent
terms on the diagonal only, reads
√
ωr
B(1
−
1 + x2 ) − √sin( 2δ ) sin(θr )

2

 √
 − ωr2 sin( 2δ ) sin(θr ) 2B − ωr cos(θr )Hdressed = 

ωr

√
0
cos( 2δ ) sin(θr )

2

ωr
−√
0
sin( 2δ ) sin(θr )
2



ωr
δ
−√
)
sin(θ
)
sin(
r 
2
2


ωr
δ
√
)
sin(θ
)
0
cos(

r
2
2
(4.43).
√ωδ
√r cos( ) sin(θr ) B(1 + 1 + x2 )

2
2

ωr
δ
√
sin(θ
)
2B
+
ω
cos(θ
)
cos(
r
r
r
2
2
0

In the limit that x  1 the diagonal terms for the two M N = 0 states are merely the(±)

quadratic Stark shift ES= ±(µm E)2 /6B. Now read off the ordinary Berry phase fromthe diagonal perturbations linear in ω r , yielding the usual
γ (0) (|Ñ MN i) = −2πMN cos(θr ),(4.44)

where by Ñ is meant the appropriate eigenstate of the field-mixed M N = 0 states [100].
This diagonalization removed the degeneracy of the M N = 0 level with the MN = ±1
levels of the N = 1 subspace. However, the degeneracy among the M N = ±1 states still
exists.
Having quasi-broken the degeneracy in the N = 1 levels, evaluation of the firstorder non-adiabatic correction term using standard second-order perturbation theory
seems a logical next step. It is evident that both states |N, M N = ±1i experience
the same additional phase at this order (due to their degeneracy in the non-perturbing
Hamiltonian), given byγ(1)(|1, ±1) = −π

6B(µm E)2ωr sin2 (θr ),(4.45)

105
where an expansion in the small parameter x has been applied. Requiring this to be asmall correction identifies the adiabaticity criterion for this situation. If this case wereanalogous to the magnetic field case, one would only be concerned about the magnitudeof ωr with respect to µm E, which is the stand-in for the Larmor frequency. However,Eqn. (4.45) suggests a slightly different criterion, namely ω r B  (µm E)2 must hold inorder to recover the simple leading-order Berry phase. To understand the origin of thiscriterion look at the term in the large parentheses in (4.45). It is the inverse of the
Stark energy in the absence of field rotation for the upper level. Now rewrite (4.45) asγ (1) (|N MN = ±1i) = −2πωrsin2 (θr ),2 ES(4.46)

and recover a form reminiscent of the pure spin case (cf. (4.19)), where the Larmor
frequency, ωL , is replaced by ES , the quadratic Stark shift. In order to be an adiabatic
correction, it is immediately evident why ω r B  (µm E)2 must hold; the rotation rate
must be small compared to the energy splitting in that level. In this case, the splitting
is quadratic in electric field and therefore a secondary energy scale — the rotational
level splitting or internal structure — must come into play.
By similar reasoning, γ (1) corrections for the MN = 0 states can be obtained aswell. That of the lower level is given by
γ (1) (|Ñ ∼ 0 , 0i) = −2πESωrsin2 (θr ),2B
2B(4.47)

where the requirement that ωr ES  B 2 must hold. In this case, our assumptions
clearly support this adiabatic criterion since the regime ω r  µm E  B is assumed.
This correction is linear in ωr , but suppressed by the ratio of the Stark energy to therotational constant of the molecule. Physically, this is because this state is far removed
from the “degeneracy” in the N = 1 levels. It is the electric analogue of the weakmagnetic field limit of the spin-spin interaction. The correction for the upper level isgiven byγ (1) (|Ñ ∼ 1 , 0i) = 4πωrsin2 (θr ).
2 ES(4.48)

106
This correction is in the opposite direction to and twice that of the |N M N = ±1i states
because the |Ñ ∼ 1 , 0i state is influenced by the two states, M N = ±1, that are below
it in energy. This is in contrast to the coupled spins in a magnetic field case, where
each MN = ±1 contributed equally in magnitude but opposite in sign. This is due tothe lack of any linear Stark shift in the M N = ±1 levels.
It is evident that polar molecules in a rotating electric field are quite similar tomagnetic dipoles in rotating magnetic fields. There is an energy splitting in comparison
with which the rotation of the field must be small to ensure adiabaticity. If there is a
shift in energy that is linear with the applied field, then the rotation rate must be small
compared to this energy. However, if the energy scales quadratically with the appliedfield, the rate of rotation must be small in comparison to the energy shift in the field.
Thus, the internal structure is quite important in regimes of quadratic field shifts andintroduces different adiabaticity requirements on ω r in terms of the applied field andinternal structure.
3

4.6
3∆

∆1 molecules

1 molecules are a whole other bag of worms. In Sec. 3.3.2 it was made apparent

that they can be quite complicated. Adding a rotating electric field to the mix will
make it even more so. However, in this section only nuclear spin free systems will beconsidered, so as to only present the necessary new physics. Recall Fig. 3.11. The uppercomponent shifts in energy with the application of an electric field. The Hamiltonian
which describes the object in the rotating field is given by
Hdress = −~µ · E~ − õ∆ J 2 δΩ,−Ω0 + BJ 2 − ωr (cos(θr )Jz − sin(θr )Jx ).

(4.49)

The first term is the Stark interaction, the second the Λ-doubling which connects statesof Ω → −Ω, the third end-over-end rotation, and the last the rotating contribution. For
P
inclusion of any J, the total number of channels in the system scales as J 2(2J + 1),

107
where the extra 2 encapsulates the two Ω’s in the problem.
The concern is primarily with the Stark degenerate states M Ω = ±1, and therefore it would be beneficial if there were a way to understand the new physics that arises
from the rotating field. I shall choose the regime where the electric field is vastly larger
than õ∆ and ωr yet ridiculously small compared to the rotational splitting given by
2B(J + 1). Therefore, the Stark energy is the dominant energy in the system. Treating the other two interactions, Λ-doubling and rotation, as small one can try to build
an effective Hamiltonian in the basis of M Ω = ±1. The reason for this is to try tounderstand the the degenerate states in terms of a 2 × 2 matrix.
The interesting item to note is that the rotating field ω r couples M to M ±1 while
Λ-doubling couples Ω = ±1 to Ω = ∓1. Thus, in a perturbative approach, it is evident
that states with M = 1, Ω = −1 are coupled at some level to states with M = −1, Ω = 1.
Yet, in Fig. 3.11, these were the states where the upper transition W u is to be measured
to determine the eEDM. This is potentially hazardous because should there ever be acase where the two states are degenerate then the rotation would introduce a complete
mixing of states, yielding new eigenfunctions proportional to |M, Ωi ± | − M, −Ωi. If theelectron being measured in the experiment spends half its time up against the applied
axis and half its time down, the effect cancels out. And apparently, when θ r = π/2
the situation is just so that the two levels are degenerate, as is evident from staring at
Eq. (4.49) long enough.
Now, in the ion trap of the JILA eEDM experiment, θ r = π/2, or at least will varyaround this choice of angle. Therefore, there will need to be some way to understandthe eigenfunctions in the plane. Because the |M Ω = ±1i states are coupled by the
combined interactions of the rotating field and Λ-doubling, the states at the value of

108
θr = π/2 are given by (in the |M Ωi basis)||M Ω|, +i =||M Ω|, −i =1
√ (|1, −1i + | − 1, 1i)
2
1√ (|1, −1i − | − 1, 1i) .
2(4.50)(4.51)Neither of these states is conducive to measuring the eEDM. Therefore, the size of theenergy splitting between these states needs to be understood as well as a way to moveback into a regime of good M and Ω.
The matrix elements of interest in a fixed J-level are given byhJM Ω|õ∆ J 2 |JM − Ωi = 2õ∆ J(J + 1)~
hJM Ω| − µ~ · E|JMΩi = −µE

MΩ
J(J + 1)

(4.52)

hJM Ω| − ωr cos(θr )Jz |JM Ωi = −ωr cos(θr )M√hJM Ω| − ωr sin(θr )Jx |JM Ωi = hJM Ω| − ωr sin(θr )(J+ + J− )/ 2|JM Ωip=(J + M )(J − M + 1)/2+
p(J − M )(J + M + 1)/2 ωr sin(θr )The raising and lowering here operators act on the laboratory defined axis of the instantaneous field, as opposed to earlier in Sec. 3.3.2.
In order to understand the energies associated with the terms in Eqs.(4.50) and(4.51), one can take a sum of the perturbative terms and raise them to the 2|M | + 1
power, then divide by ∆E 2M . This is because the order at which the two states arecoupled requires 2|M | applications of the rotating field and one application of the Λdoubling term.
Hpeturb ∝(HΛD + Hrot field )2|M |+1
∆E 2M
2|M |

∝ HΛD Hrot field + permutations.

(4.53)The permutations have to deal with whether the Λ-doubling occurs first, second, or
third. In fact, there are 2|M | + 1 permutations in general. In the case of 3 ∆1 with no

109
2
2
hyperfine, this reduces to HΛD Hrot
field , Hrot field HΛD Hrot field , and Hrot field HΛD . One

must account for each term because the energy denominators are different in each case.
To illustrate, the first term takes (using |M Ωi basis functions) |11i → |01i → | − 11i →| − 1 − 1i. The second term is |11i → |01i → |0 − 1i → | − 1 − 1i. These multiple
paths can constructively or destructively interfere with each other, and therefore mustbe accounted for separately.
The energy denominators are given by either M − (M ± 1) or ±2Ω times the the
Stark parameter µE/(J(J + 1)). Using some algebra one arrives at an expression forthe matrix element connecting |M Ωi to | − M − Ωi (at θ r = π/2)hM Ω|Hpeturb | − M − Ωi = y[J, M ]õ∆



ωr
µE

2|M |.

(4.54)

The function y[J, M ] depends on the many ways in which the operators can act and inwhat order. It is not enlightening to write down the form since it is merely a complicatedexpression, however in the case of 3 ∆1 ground state molecules, y[J, M ] = 16. What isenlightening is that the interaction has a scaling law. The larger the value of M inwhich one starts, the smaller is the term which couples |M, Ωi to | − M, −Ωi. In theabsence of Λ-doubling or field rotation there is no coupling between these states. It isan artifact of the combined effects.
It is worth noting that the way in which the interaction was developed is entirely
akin to the way in which one creates the effective Hamiltonian for Λ-doubling, of theregular, hyperfine induced, or Zeeman induced varieties. In the plane of rotation defined by θr = π/2, this method lends itself to being dubbed M Ω-doubling (pronounced“momega”-doubling), because states with the same value of M Ω are degenerate andsplit by an “effective” parity interaction. This parity is related to the sense of rotationin cahoots with the orientation of the molecular axis. An outward pointing Ω (dipole
moment of the molecule pointing along instantaneous field direction) with an outward
M rotating in a positive sense is degenerate with an inward Ω, inward M rotating in a

110positive sense. If one were to look at the case of magnetic spins and bring Ω into thedefinition of the g-factor, then the two states have equal and opposite g-factors suchthat a positive g-factor for state M for all intents and purposes is the same as a negative
g-factor for state −M .
In the basis of |M Ωi, the effective 2 × 2 Hamiltonian describing the interaction
between the degenerate Stark states near the value θ r = π/2 is



ωr 2
dE
+
ω
α
16
õ
r
∆ 
dE
 2
H2×2 = 
,

ωr 2
dE
16 dE
õ∆
−
ω
α
r
2

(4.55)

where the small angle approximation has been applied and α = θ r − π/2. Now, should

one want to “push” the crossing to a different value of α so as to be able to do theexperiment at θr = π/2, one would have to shift the M = 1 and M = −1 level in
addition to the shift that is applied by α. The Zeeman interaction does this because it
does not care about the sign of M Ω, just the sign of M . Therefore, applying a magnetic
field collinear with the electric field will shift the crossing to a different value of α. The
Hamiltonian in Eq. (4.55) is modified such thatg J µB B
ωr 2dE
16 dE õ∆
 2 + 2 + ωr α
H2×2 = ,g J µB B
ωr 2
dE
16 dE
−
−
ω
α
õ∆
r
2
2

(4.56)

where gJ = (gL Λ − gS Σ)Ω. Now, the new value α where the coupling is maximal and|M Ωi states are degenerate isα=−gJ µB B.
2ωr

(4.57)

Recall that the value of gJ ≈ 0.1. Now, in the proposed experiment the ratio of the
Zeeman energy to ωr is expected to be around 0.012 [78]. Thus, the angle is shifted anamount α = 0.06, which is small enough that the small angle approximation still holds.
What remains to be seen is whether a shift this small brings one back to the regime ofgood M and Ω at the value of α = 0.
This crossing, as a function of α is presented in Fig. 4.3. The upper panel(Eq. (4.55) solutions) shows the avoided crossing. The units on the x-axis are in terms

111

E HgJ ΜB B2Ωr L

1

0

-1

E HgJ ΜB B2Ωr L

1

0

-1
-3

-2

-1
0
1
Α HgJ ΜB B2Ωr L

2

3

Figure 4.3: The upper panel shows the avoided crossing for a purely Stark interaction.
At α = 0 (corresponds to θr = π/2), the two states are maximally mixed, which is badfor an eEDM measurement. However, the application of a magnetic field will move thecrossing to a new value of α that is governed by the ratio of the Zeeman energy to thefield rotation energy (bottom panel).

112
of gJ µB B/2ωr , and on the y-axis the energy has been offset so as to center the crossing
around zero. The units on the y-axis are in terms g J µB B/2ωr as well. The applicationof a magnetic field, which like the rotation of the electric field acts only on M , will movethe degeneracy to a different value of α = g J µB B/2ωr . Now, to determine whether the
eigen-states at α = 0 are states of good M and Ω one compares the energy difference
between the states |1 − 1i and | − 11i (in the |M Ωi) basis to the strength of the coupling|gJ µB B|  16 ω 2
r

dE

õ∆ ,

(4.58)

which is met in the proposed experiment [78]. The LHS of Eq. (4.58) has the valueof gJ µB B ≈ 2.5 kHz while the RHS has the value 0.25 kHz, or a factor of 10 smaller.
Thus, the values of M and Ω are fairly good in this regime.
By applying the magnetic field to shift the location of the crossing to values ofθr 6= π/2, one recovers states of good M and good Ω in the plane defined by θ r = π/2.
Now, should the ions oscillate up and down across this plane, as ions in an ion trap
invariably do, they will not experience this crossing provided the amplitude of theoscillation is less than |αosc |  0.06. The axial electric field is expected to cause
oscillations in |αosc | ≈ 0.0005, from the parameters in the proposed experiment [78].
Therefore, the ability to perform an eEDM measurement on molecular ions in an ion
trap is completely feasible.
One item to note is that in the proposed experiment, there is hyperfine structure,
which makes the total angular momentum basis F = 3/2 in the ground state. In thisstate, MF = 3/2 is the total M and this further reduces the size of the coupling strength.
The Stark and Zeeman energies will be comparable up to a geometric factor describing
the coupling of the spins J to F . Therefore, the extra complexity of hyperfine structure
actually helps to alleviate the symptomatic effects of rotating in the plane θ r = π/2 byfurther reducing the coupling strength between states of |M Ωi and | − M − Ωi.

Chapter 5. . . In the End

The best way to be boring is to leave nothing out.
– Francois Voltaire
And now you are either wondering what it is I have left out, or you are reallybored. I do hope it is the former.

5.1

A mild review
In this thesis I have presented three ideas all linked by their goal to understanddiatomic molecular candidates for an eEDM search. Perturbation theory played a pivotal role in understanding the estimation of E eff . Standard ab initio techniques wereused to create potential energy surfaces for the new candidates and these surfaces werein turn used to place a size on the interactions that lead to spectroscopic observables.
The theory of Λ-doubling was extended to the hyperfine realm by applying perturbative
rules and scaling laws. While the spectroscopy of 3 ∆ molecules may be complicated,each term can be understood by applying simple arguments. The goal of understanding
even the most minute detail of the spectroscopy is to isolate the spectroscopic shift
due to an eEDM. Finally, a dressed state approach to Berry’s phase was developed toaddress the effects of structure on the additional phases. The role that structure plays
is to systematically shift the levels of interest in an eEDM experiment, but in such a
way for which it is easily accounted.

114

5.2

The future
There are other avenues to explore EDM effects. An interesting one with molecules

is to search for the neutron or proton EDM (nEDM, where n stands for nucleon). 1 Σmolecules such as TlF have been proposed as candidates for measuring the nEDM andmeasurements have been made [106]. Here I offer a slightly different approach. Great
work has been performed on 199 Hg as an atomic candidate for a nEDM search [107].
Since Hg can be laser cooled as well as Sr, one may consider HgSr a viable candidate
for a nEDM search in its 1 Σ ground state because the molecule has the possibility to
be produced at ultracold temperatures. The Sr atom acts as a “handle” by which themolecule can be polarized. There is much work to be done regarding this field, but
it is but one example of the use of molecules in precision studies. The same ab initio
methods employed to calculate the wave functions in for the 3 ∆ molecules can be used
to construct the wave functions for the 1 Σ candidates.
A further examination of Berry’s phase in a dressed state picture can also be
explored. Currently, only time-variations in the angle φ, the azimuthal angle, havebeen explored. One can imagine simple time-dependent θ models which would also leadto additional phases. Trying to understand simple oscillations in θ would be an ideal
next step since these oscillations occur in ion trap environments. This oscillation would
effectively take the system through the avoided crossing in Fig. 4.3 and one can ask how
the time scale of this oscillation will affect an eEDM search.

Bibliography[1] I.I. Bigi and A.I. Sanda. CP Violation. Cambridge university press, 2000.
[2] T.E. Browder and R. Faccini. Establishment of cp violation in b decays. Ann.
Rev. Nucl. Part. Sci., 53:353, 2003.
[3] J. Schwinger. On guage invariance and vacuum polarization. Phys. Rev., 82:664,
1951.
[4] N.F. Ramsey. Electric-dipole moments of particles. Ann. Rev. Nucl. Part. Sci.,
32:211, 1982.
[5] I.B. Khriplovich and S.K. Lamoreaux.
Springer-Verlag, Berlin, 1997.

CP Violation without Strangeness.

[6] W. Bernreuther and M. Suzuki. Electric dipole moment of the electron. Rev.
Mod. Phys., 63:313, 1991.
[7] B.C. Regan, E.D. Commins, C.J. Schmidt, and D. DeMille. New limit on theelectron electric dipole moment. Phys. Rev. Lett., 88:071805, 2002.
[8] M.E. Peskin and D.V. Schroeder. An Introduction to Quantum Field Theory.
Westview Press, USA, 1995.
[9] Sarah Bickman. Progress Towards a Measurement of the Electric Dipole Momentof the Electron using PbO∗ . PhD thesis, Yale University, 2007.
[10] D. DeMille, S. Bickman, P. Hamilton, Y. Jiang, V. Prasad, and R. Paolina. Search
for the electron electric dipole moment. In Particles and nuclei international
conference, number 669 in 842. AIP, 2005.
[11] F.J. Gilman, K. Kleinknecht, and B. Renk. The cabibbo-kobayashi-maskawa
quark mixing matrix. Review of Particle Physics, Physics Letters B, 592:1, 2004.
[12] P.G.H. Sandars. The electric dipole moment of an atom i: Some general considerations. J. Phys. B, 1:499, 1968.
[13] P.G.H. Sandars. The electric dipole moment of an atom ii: The contribution froman electric-dipole moment of the electron with particular reference to the hydrogenatom. J. Phys. B, 1:511, 1968.

116[14] J.J. Hudson, B.E. Sauer, M.R. Tarbutt, and E.A. Hinds. Measurement of theelectron electric dipole moment using ybf molecules. Phys. Rev. Lett., 89:023003,
2002.
[15] R. Stutz and E. Cornell. Bull. Am. Soc. Phys., 49:76, 2004.
[16] J. Brown and A. Carrington. Rotational Spectroscopy of Diatomic Molecules.
Cambridge University Press, Cambridge, 2003.
[17] L.I. Schiff. Measurability of nuclear electric dipole moments. Phys. Rev., 132:2194,
1963.
[18] M. V. Berry, F.R.S. Quantal phase factors accompanying adiabatic changes.
Proc. R. Soc. Lond. A, 382:45–57, 1984.
[19] L.L Foldy and S.A. Wouthuysen. On the dirac theory of spin 1/2 particles andits non-relativistic limit. Phys. Rev., 78:29, 1950.
[20] J.D. Bjorken and S.D. Drell. Relativistic Quantum Mechanics. McGraw-Hill, New
York, 1964.
[21] V.B. Berestetskii, E.M. Lifshitz, and L.P. Pitaevskii. Quantum Electrodynamics.
Pegamon Press, Oxford, 1982.
[22] U. Fano, C.E. Theodosiou, and J.L. Dehmer. Electron-optical properties of atomic
fields. Rev. Mod. Phys., 48:49, 1976.
[23] E.M. Purcell and N.F. Ramsey. On the possibility of electric dipole moments forelementary particles and nuclei. Phys. Rev., 78:807, 1950.
[24] R.L. Garwin and L.M. Lederman. Nuovo Cim., 11:776, 1959.
[25] E.D. Commins, J.D. Jackson, and D.P. DeMille. The electric dipole moment of
the electron: An intuitive explanation for the evasion of schiff’s theorem. Am. J.
Phys., 75:532, 2007.
[26] P.G.H. Sandars. The electric dipole moment of an atom. Phys. Lett., 14:194,
1965.
[27] P.G.H. Sandars. Enhancement factor for the electric dipole moment of the valence
electron in an alkali atom. Phys. Lett., 22:290, 1966.
[28] E.R. Meyer, M.P. Deskevich, and J.L. Bohn. Candidate molecular ions for anelectron electric dipole moment experiment. Phys. Rev. A, 73:062108, 2006.
[29] E.A. Hinds. Probing the electron edm with cold molecules. Phys. Sc., T, T70:34,
1997.
[30] E.D. Commins. Electric dipole moments of leptons. Adv. in At., Mol., and Opt.
Physics, 40:1, 1999.
[31] E.N. Fortson, P.G.H. Sandars, and S. Barr. The search for a permanent electric
dipole moment. Physics Today, June:33, 2003.

117[32] A.C. Hartley, E. Lindroth, and A.-M. Mårtensson-Pendrill.
Parity nonconservation and electric dipole moments in caesium and thallium. J. Phys. B,
23:3417, 1990.
[33] V.V. Flambaum. Sov. J. Nucl. Phys., 24:383, 1976.
[34] Z.W. Liu and H.P. Kelly. Analysis of atomic electric dipole moment in thallium by
all order calculations in many-body perturbation theory. Phys. Rev. A, 45:R4210,
1992.
[35] E.R. Meyer and J.L. Bohn. Prospects for an electron electric dipole moment searchin tho and thf+ . Phys. Rev. A, 78:010502(R), 2008.
[36] E.R. Meyer and J.L. Bohn. Electron electric dipole moment searches based on
alkali-metal or alkaline-earth-metal bearing molecules. Phys. Rev. A, 80:042508,
2009.
[37] M.G. Kozlov, A.V. Titov, N.S. Mosyagin, and P.V. Souchko. Enhancements ofthe electric dipole moment of the electron in the baf molecule. Phys. Rev. A,
56:R3326, 1997.
[38] Y.Y. Dmitriev et al. Calculation of the spin-rotational hamiltonian including p−
and t− odd weak interaction terms for hgf and pbf molecules. Phys. Lett. A,
167:280, 1992.
[39] A.N. Petrov, A.V. Titov, T.A. Isaev, N.S. Mosyagin, and D. DeMille. Configuration interaction calculation of the hyperfine and p,t-odd constants on the 207 pbo
excited states for electron electric dipole moment experiments. Phys. Rev. A,
72:022505, 2005.
[40] T.A. Isaev, N.S. Mosyagin, A.N. Petrov, and A.V. Titov. In search of the electron
electric dipole moment: Relativistic correlation calculations of the p, t-violating
effect in the ground state of hi+ . Phys. Rev. Lett., 95:163004, 2005.
[41] A.N. Petrov, N.S. Mosyagin, T.A. Isaev, and A.V. Titov. Theoretical study ofhff+ in search of the electron electric dipole moment. Phys. Rev. A, 76:030501(R),2007.
[42] J. Lee, E.R. Meyer, R. Paudel, J.L. Bohn, and A.E. Leanhardt. An electron electric
dipole moment search in the x3 δ1 ground state of tungsten carbide molecules. J.
Mod. Opt., 56:2005, 2009.
[43] M.J. Seaton. Quantum defect theory. Rep. Prog. Phys., 46:167, 1983.
[44] U. Fano and A.R.P. Rau. Atomic collisions and spectra. Academic Press, Inc.,New York, 1986.
[45] H.-J. Werner, P. J. Knowles, R. Lindh, F. R. Manby, M. Schütz, et al. Molpro,
version 2008.3, a package of ab initio programs, 2008. see http://www.molpro.net.
[46] D. Feller. J. Comp. Chem., 17:1571, 1996. see https://bse.pnl.gov/bse/portal.

118[47] various authors.
Institut for theoretical chemistry, 2010.
http://www.theochem.uni-stuttgart.de/pseudopotentials/index.en.html.

see[48] H.-J. Werner and P.J. Knowles. A second order multiconfiguration scf procedure
with optimum convergence. J. Chem. Phys., 82:5053, 1985.
[49] P. J. Knowles and H.-J. Werner. An efficient second-order mccsf method for long
configuration expansions. Chem. Phys. Lett., 115:259, 1985.
[50] H.-J. Werner and W. Meyer. A quadratically convergent multiconfiguration–selfconsistent field method with simultaneous optimization of orbitals and ci coefficients. J. Chem. Phys., 73:2342, 1980.
[51] H.-J. Werner and W. Meyer. A quadratically convergent mcscf method for thesimultaneous optimization of several states. J. Chem. Phys., 74:5794, 1981.
[52] H.-J. Werner. Adv. Chem. Phys., LXIX:1, 1987.
[53] H.-J. Werner and P.J. Knowles.
An efficient internally contracted
multiconfiguration–reference configuration interaction method. J. Chem. Phys.,
89:5803, 1988.
[54] P.J. Knowles and H.-J. Werner. An efficient method for the evaluation of coupling
coefficients in configuration interaction calculations. Chem. Phys. Lett., 145:514,
1988.
[55] H.-J. Werner and E.A. Reincsh. The self-consistent electron pairs method for
multiconfiguration reference state functions. J. Chem. Phys., 76:3144, 1982.
[56] A. Berning, M. Schweizer, H.-J. Werner, P. J. Knowles, and P. Palmieri. Mol.
Phys., 98:1823, 2000.
[57] Y. Wang and M. Dolg. Pseudopotential study of the ground and excited states ofyb2 . Theor. Chem. Acc., 100:124, 1998.
[58] Jr. T.H. Dunning. Gaussian basis sets for use in correlated molecular calculations.
i. the atoms boron through neon and hydrogen. J. Chem. Phys., 90:1007, 1989.
[59] L.v. Szentpaly, P. Fuentealba, H. Preuss, and H. Stoll. Psuedopotential calculations on rb+
2.
[60] P. Fuentealba, H. Stoll, L.v. Szentpaly, P. Schwerdtfeger, and H. Preuss. On
the reliability of semi-empirical pseudopotentials: simulation of hartree-fock anddirac-fock results. J. Phys. B, 16:L323, 1983.
[61] V.V. Van Vleck. On σ-type doubling and electron spin in the spectra of diatomic
molecules. Phys. Rev., 33:467, 1929.
[62] J.L. Dunham. The energy levels of a rotating vibrator. Phys. Rev., 41:721, 1932.
[63] J.K.G. Watson. The isotope dependence of diatomic dunham coefficients. J. Mol.
Spect., 80:411, 1980.

119[64] J. Wang B.E. Sauer and E.A. Hinds. Laser-rf double resonance spectroscopy of
174 ybf in the x2 σ + state: Spin-rotation, hyperfine interactions, and the elctric
dipole moment, journal =.
[65] A.R. Edmonds. Angular Momentum in Quantum Mechanics. Princeton University
Press, Princeton, 1960.
[66] M.E. Rose. Elementary Theory of Angular Momentum. John Wiley and Sons,
Inc., New York, 1957.
[67] D.M. Brink and G.R. Satchler. Angular Momentum. Oxford University Press,
Oxford, 1962.
[68] D. DeMille, F. Bay, S. Bickman, D. Kawall, Jr. D. Krause, S.E. Maxwell, and
L.R. Hunter. Investigation of pbo as a system for measuring the electric dipole
moment of the electron. Phys. Rev. A, 61:052507, 2000.
[69] D. Figgen, K.A. Peterson, M. Dolg, and H. Stoll. J. Chem. Phys., 130:164108,
2009.
[70] W. Kuechle, M. Dolg, H. Stoll, and H. Preuss. Energy adjusted pseudopotentials
for the actinides. parameter sets and test calculations for thorium and thoriummonoxide. J. Chem. Phys., 100:7535, 1994.
[71] X. Cao, M. Dolg, and H. Stoll. Valence basis sets for relativistic energy-consistentsmall-core actinide pseudopotentials. J. Chem. Phys., 118:487, 2003.
[72] X. Cao and M. Dolg. Segmented contraction scheme for small-core actinide pseudopotential basis sets. J. Molec. Struct. (Theochem), 673:203, 2004.
[73] A.C. Vutha et al. Search for the electric dipole moment of the electron withthorium monozide. ArXiV:0908.2412v1, 2009.
[74] C. E. Moore. Atomic Energy Levels, Circ. 467. Vol. III. Natl. Bur. Stand. (U.S.),
1958.
[75] J.M. Brown, A.S-C. Cheung, and A.J. Merer. λ-type doubling parameters formolecules in δ electronic states. J. Mol. Spec., 124:464, 1987.
[76] T.C. Steimle, D.F. Nachman, J.E. Shirley, D.A. Fletcher, and J.M Brown. The
microwave spectrum of nih. Mol. Phys., 9:923, 1990.
[77] T. Nelis, S.P. Beaton, K.M. Evenson, and J.M Brown. A determination of themolecular parameters for nih in its 2 δ ground state by laser magnetic resonance.
J. Mol. Spectr., 142:462, 1991.
[78] R. Stutz et al. On measuring the electron electric dipole moment in trappedmolecular ions. In preparation, 2010.
[79] B. Simon. Holonomy, the quantum adiabatic theorem, and berry’s phase.
Phys. Rev. Lett., 51(24):2167–2170, 1983.

120[80] J. Anandan and L. Stodolsky. Some geometrical considerations of berry’s phase.
Phys. Rev. D, 35(8):2597–2600, 1987.
[81] Y. Aharonov and J. Anandan. Phase change during a cyclic quantum evolution.
Phys. Rev. Lett., 58(16):1593–1596, 1987.
[82] D. N. Page. Geometrical description of berry’s phase. Phys. Rev. A, 36(7):3479–
3481, 1987.
[83] J. C. Garrison and E. M. Wright. Complex geometrical phases for dissipative
systems. Phys. Lett. A, 128(3,4):177–181, 1988.
[84] J. M. Robbins and M. V. Berry. A geometric phase for m = 0 spins. J. Phys. A:
Math. Gen., 27:L345–L348, 1994.
[85] M. V. Berry, F.R.S. Quantum phase corrections from adiabatic iteration.
Proc. R. Soc. Lond. A, 414:31–46, 1987.
[86] M. V. Berry, F.R.S.
Histories ofProc. R. Soc. Lond. A, 469:61–72, 1990.

adiatbatic

quantumtransitions.

[87] M. V. Berry, F.R.S. Geomtric amplitude factors in adiabatic quantum transitions.
Proc. R. Soc. Lond. A, 430:405–411, 1990.
[88] Shi-Min Cui. Nonadiabatic berry phase in rotating systems. Phys. Rev. A,
45(7):5255–5237, 1992.
[89] J. H. Hannay. The berry phase for spin in the majorana representation. J. Phys.
A: Math. Gen., 31:L53–L59, 1998.
[90] D. J. Moore. Berry phases and hamiltonian time dependence. J. Phys. A: Math.
Gen., 23:5523–5534, 1990.
[91] D. J. Moore. The calculation of nonadiabatic berry phases. Physics Reports,
210(1):1–43, 1991.
[92] D. J. Moore. Floquet theory and the nonadiabatic berry phase. J. Phys. A: Math.
Gen., 23:L665–L668, 1990.
[93] D. J. Moore and G. E. Stedman. Adiabatic and nonadiabatic berry phase for
two-level atoms. Phys. Rev. A, 45(1):513–519, 1991.
[94] S. A. R. Horsley and M. Babiker. Topological phases for composite particles withdynamic properties. Phys. Rev. Lett., 99:090401, 2007.
[95] F. Wilczek and A. Zee. Appearance of gauge strucure in simple dynamical systems.
Phys. Rev. Lett., 52(24):2111–2114, 1984.
[96] J. E. Avron, R. Seiler, and L. G. Yaffe. Adiabatic theorems and applications to
the quantum hall effect. Commun. Math. Phys., 110:33–49, 1987.
[97] Z.-C. Wang and B.-Z. Li. Geometric phase in relativistic quantum theory.
Phys. Rev. A, 60(6):4313–4317, 1999.

121[98] J. de Boer, K. Papadodimas, and E. Verlinde. Black hole berry phase. Phys. Rev.
Lett., 103:131301, 2009.
[99] P. Hoodbhoy. Berry’s phase for atomic levels. Phys. Rev. A, 38(7):3766–3768,
1988.
[100] A. Vutha and D. DeMille. Geometric phases without geometry. ArXiV:0907.5116,
pages 1–8, 2009.
[101] C. Cohen-Tannoudji, J. Dupont-Roc, and G. Grynberg.
Interactions. John Wiley & Sons, Inc., New York, 1992.

Atom-Photon[102] D. M. Brink and G. R. Satchler. Angular Momentum, 3 rd Ed. Clarendon Press,
Oxford, 1993.
[103] S. Appelt, G. Wäckerle, and M. Mehring. Deviation from berry’s adiabatic geometric phase in a 131 Xe nuclear gyroscope. Phys. Rev. Lett., 72(25):3921–3924,
1994.
[104] E. Sjöqvist, X. X. Yi, and J. Âberg. Adiabatic geomtric phases in hygrogenlike
atoms. Phys. Rev. A, 72:054101, 2005.
[105] S. Oh, Z. Huang, U. Preskin, and S. Kais. Entaglement, berry phases, and levelcrossings for the atomic breit-rabi hamiltonian. Phys. Rev. A, 78:062106, 2008.
[106] E.A. Hinds, C.E. Loving, and P.G.H. Sandars. Phys. Lett. B, 62:97, 1976.
[107] W.C. Griffith, M.D. Swallows, T.H. Loftus, M.V. Romalis, B.R. Heckel, and E.N.
Fortson. Improved limit on the permanent electric dipole moment of 199 hg. Phys.
Rev. Lett., 102:101601, 2009.

Appendix A

Sample molpro input

If you put tomfoolery into a computer, nothing comes out of it except tomfoolery. But
this tomfoolery, having passed through a very expensive machine, is somehow ennobled
and no one dares criticize it.
–Pierre Gallois
The items which appear in verbatim are actually coding scripts. The dialog thatis in between is for explanation as well as troubleshooting common errors.

The first thing to do is call the memory requirements. Often, one gets an error
message along the lines of “not enough memory, require ### words and have ###words.” If this is the case, just increase the memory. “Words” is related to bits, and is
not the unit you need. Play around with it until the error message goes away.
memory,2500,m
gprint,orbital,civector;
The second line informs the program that you would like to have the orbitals and theci-vector coefficients printed for every HF, MCSCF and MRCI calculation.
Next one must define the basis sets of interest. This is for ThF + .
basis

123
f=avtz;ecp,th,ecp60mwb;
spdfg,th,ecp60mwb_seg;
endThis calls the aug-cc-pVTZ basis for F and the ECP60MWB effective core potential andbasis set for Th. The “seg” refers to segmented and means this basis can be used forspin-orbit calculations. If the basis set is not known in molpro, then one can import
the basis by copying from the Stuttgart website [47] for heavy elements.
Now it is time to set the geometrygeometryf;th,f,r(i);endrlist=[1,2,3,4,5,6,7] bohr;
This geometry is in Z-matrix format. It says to place the Th atom from the F atom a
distance r(i) away, where r(i) will be defined via a call to “rlist.”
Now one is ready to calculate the meaty part. First, set the counter to zero,then start chugging away at steps. Go from the first element to the last in “rlist” inincrements of 1. Define the “ith ” element of r(i) as the “ith ” element of “rlist.” I will
break it up into the RHF-MCSCF and the the MRCI+SO sections.
i=0;
do ith=1,#rlist
i=i+1
r(i)=rlist(ith);{hf;start,atden;
wf,38,1,0;}124{multi;frozen,2,1,1,0;closed,8,3,3,1;occ,11,4,4,2;
wf,38,1,0;
wf,38,1,2;wf,38,4,2;}{multi;closed,8,3,3,1;occ,11,4,4,2;
wf,38,1,0;
wf,38,1,2;wf,38,4,2;}{multi;closed,8,3,3,1;occ,12,5,5,2;
wf,38,1,0;state,2;wf,38,4,0;
wf,38,1,2;state,2;wf,38,4,2;
wf,38,2,0;wf,38,3,0;
wf,38,2,2;wf,38,3,2;}{multi;closed,8,3,3,1;occ,13,6,6,2;
wf,38,1,0;state,2;wf,38,4,0;
wf,38,1,2;state,2;wf,38,4,2;
wf,38,2,0;wf,38,3,0;
wf,38,2,2;wf,38,3,2;}{multi;closed,8,3,3,1;occ,13,6,6,2;
wf,38,1,0;state,3;wf,38,4,0;
wf,38,1,2;state,2;wf,38,4,2;state,2;
wf,38,2,0;wf,38,3,0;
wf,38,2,2;state,2;wf,38,3,2;state,2;}{multi;closed,8,3,3,1;occ,13,6,6,2;
wf,38,1,0;state,5;wf,38,4,0;state,3;
wf,38,1,2;state,3;wf,38,4,2;state,3;
wf,38,2,0;state,2;wf,38,3,0;state,2;
wf,38,2,2;state,2;wf,38,3,2;state,2;}{multi;closed,8,3,3,1;occ,13,6,6,2;maxiter,25;

125
wf,38,1,0;state,5;wf,38,4,0;state,3
wf,38,1,2;state,3;wf,38,4,2;state,3;
wf,38,2,0;state,2;wf,38,3,0;state,2;
wf,38,2,2;state,2;wf,38,3,2;state,2;}
Each subsequent step in the MCSCF (or “multi”) is to gradually build wave functions
from the ground up starting with a calculation on 1 Σ and 3 ∆, then adding progressively
more spin multiplicities and spatial symmetries. The “wf,38,Sym,2*Spin” commandlines are organized such that the pieces with degenerate spatial and spin multiplicities
are next to each other. In the MRCI terms below, the energy values are stored inparameters. For brevity, I have only included one label, but one can save multiple. The
save command stores the orbital to be used in a spin-orbit calculation later when the“ci;hlsmat,ecp. . . ” command is entered. “ref” commands call the reference symmetries
which are degenerate with the symmetry in the given MRCI calculation.
{ci;core,8,3,3,1;
wf,38,1,0;state,5;ref,4;options,maxit=50;save,6010.2;}
esig(i)=Energy(1);{ci;core,8,3,3,1;
wf,38,1,2;state,3;ref,4;options,maxit=50;save,6110.2}{ci;core,8,3,3,1;
wf,38,4,2;state,3;ref,1;options,maxit=50;save,6210.2;}{ci;core,8,3,3,1;
wf,38,2,2;state,2;ref,3;options,maxit=50;save,6310.2}{ci;core,8,3,3,1;
wf,38,3,2;state,2;ref,2;options,maxit=50;save,6410.2;}{ci;core,8,3,3,1;
wf,38,2,0;state,2;ref,3;options,maxit=50;save,6510.2}

126{ci;core,8,3,3,1;
wf,38,3,0;state,2;ref,2;options,maxit=50;save,6610.2;}{ci;core,8,3,3,1;
wf,38,4,0;state,3;ref,1;options,maxit=50;save,6710.2}{ci;
hlsmat,ecp,6010.2,6110.2,6210.2,6310.2,6410.2,6510.2,6610.2,6710.2;
print,vls=0,hls=0}
so1(i)=Energy(1);table,r,esig,so1,...
digits,#,#,#,#...
save,filename.txt,new;enddo
The final command is to store the energies into a file named “filename.txt” and to
rewrite the file after each loop. The line “digits...” tells how many digits after thedecimal place to keep in each variable.
The common error messages that one finds are related to the “occ” and “closed”
cards. Sometimes, through misunderstandings, a user might not give the appropriate
number of occupied orbitals and the MCSCF will freak out because it cannot possibly
perform the requested calculation. If this is the case, merely think logically and add tothe occupied card. Add wisely because an increase in this number will greatly increase
computational time. If the error message is ambiguous, and just seems to exit, it islikely that the “closed” space is such that only one, or possibly zero, electrons are left
in the “active” space, defined as occ-closed. An MRCI calculation cannot do anything
if there is only one, or zero, electron(s). This is because there is nothing to correlate.
This file would calculate all the states arising from the s 2 , sd, and d2 atomic

127
orbital configuration on the Th2+ core. Recall that this will only work near the bottomof the potential wells. The larger the value of r(i), the more these states approacheach other and the more likely tiny energy differences will cause severe problems in thecalculation. Think smart, but more importantly, think efficient. I carried the calculation
to a point of first failure and then stopped. These are the curves presented in Fig. 3.8 b.

Appendix B

Pure S appendix

In Sec. 4.3, there was a Hamiltonian of the form
H = ωL Sz − ωr (cos(θr )Sz − sin(θr )Sx ),which looks like



(B.1)



0
0
... 
 a1 c1..  c1 a2 c2
0
. 




.
.

..
.. c
H=
n−2  ,
 0 c2



 ..

 .
0
c
a
c
n−2
n−1
n−1




... 0
0
cn−1 an .

(B.2)

In this system, not only is this matrix symmetric, it contains the following added symmetry: a1 = −an , a2 = −an−1 , etc. Also, the coupling coefficients c i follow a similar
property: c1 = cn−1 , etc. These properties are key to simplifying the eigenvalues of thetridiagonal matrix in this case.
Eigenvalues of an n×n tridiagonal matrix are given by the roots of the polynomial

129
pn , defined recursively by
p0 (λ) = 1,
p1 (λ) = (a1 − λ),p2 (λ) = (a2 − λ)p1 (λ) − c21 p0 (λ)..
.
pn (λ) = (an − λ)pn−1 (λ) − c2n−1 pn−2 (λ).

(B.3)

Here the constants are defined as
am = m(ωL − cos(θr )),


S 
 S 1
cm ∼ 
.
−m q m − q

(B.4)

(B.5)

Thus, the symmetry pops right out.

A simple example is the case of S = 1/2. The characteristic polynomial is11p2 (λ) = (λ − a)(λ + a) −
2
2



1
b
2

2

1
= (λ2 − (a2 + b2 ))
4

(B.6)

where a = (ωL − ωr cos(θr )) and b = ωr sin(θr ). For the case of S = 1 a similar equation(after simplification)
p3 (λ) = λ((λ − a)(λ + a) − 2= λ(λ2 − (a2 + b2 ))



1
√ b
2

2

)
(B.7)

For integer values there is always a diagonal element that is 0. As is evident, this has
the same form as (B.6) with the added piece of λ multiplying everything yielding aneigenvalue of 0. In addition, Eq. (B.7) is scaled by a factor of 4 from from Eq. (B.6),
thus making the the eigenvalues a factor of 2 larger. This is because the value of m in(B.7) is twice as large as the value of m in (B.6).

130
We can generalize the characteristic polynomial to a very simple expression due
to the added symmetries. It is given by
p2S+1 =

mY
max

m=(mmin ≥0)(λ2(1−δmmin ,0 ) − m2 (a2 + b2 )).

(B.8)

The Kronecker δ-function in (B.8) is to insure that in the event m min = 0 there is only
one eigenvalue λ = 0.