High-Order Harmonic Spectroscopy of Molecular
Structure and Dynamics
byXibin Zhou
B.S., University of Science and Technology of China, 2003
M.S., University of Colorado, 2008

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
2009This thesis entitled:
High-Order Harmonic Spectroscopy of Molecular Structure and Dynamics
written by Xibin Zhou
has been approved for the Department of Physics

Prof. Margaret M. Murnane

Prof. Henry C. Kapteyn

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
Zhou, Xibin (Ph.D., Physics)
High-Order Harmonic Spectroscopy of Molecular Structure and Dynamics
Thesis directed by Prof. Margaret M. Murnane and Prof. Henry C. Kapteyn

The recent developments of high repetition rate and high average power ultrafast
laser open the door for probing molecular structure and dynamics with intense laser
fields. In this regime, the electric field of the laser is comparable to the binding fieldof the electron in the outer valence shell of atoms or molecules. Thus the potential isstrongly modified by the laser electric field as compared to field-free atomic or molecularpotential, and the probability for ionization is dramatically enhanced.
High harmonic generation (HHG), as an ionization-initiated strong field process,can be explained well by the semiclassical recollision model. In this work, we demonstrate HHG as a new spectroscopic method for determining the molecular structure of
simple linear molecules (such as N2 and CO2 ), and for monitoring the real-time molecular dynamics of polyatomic molecules (such as N2 O4 ).
First, we use an extreme-ultraviolet interferometry to measure the phase of highorder harmonic generation from transiently aligned CO2 molecules. We unambiguously
observe a reversal in phase of the high order harmonic emission for higher harmonicorders with a sufficient degree of alignment. This results from molecular-scale quantum
interferences between the molecular electronic wave function and the re-colliding electron as it recombines with the molecule, and it is consistent with a plane wave model.
We also perform similar experiments with N2 molecules and observe behaviors that can
not be predicted by the plane-wave model.
Second, we perform an accurate polarimetry measurement of high harmonic emission from aligned molecules. Surprisingly, we find that harmonic emission from N2
molecules can be strongly elliptically polarized even when driven by linearly polarized

iv
laser fields. We extract the phase difference between the parallel and perpendicularcomponents of the high harmonic field, which strongly depends on the harmonic order. This nontrivial phase indicates a breakdown of plane wave approximation. This
work also shows that it is possible to engineer the polarization properties of harmonic
emission by carefully preparing a molecular medium.
Finally, we show that high harmonic emission can reveal coupled electronic andnuclear dynamics in polyatomic molecules. By exciting large amplitude and relative slow
vibrations in the N2 O4 molecule, we show that tunnel ionization accesses the groundstate of the ion at the outer turning point of the vibration, whereas the first excited stateis populated at the inner turning point of the vibration motion. This state switching
due to the coupled electronic and nuclear motions is manifested as bright bursts of highharmonic light that are emitted mostly at the outer turning point of the vibration, due
to the different symmetries of the ground state and the first excited state of the cation.

Dedication

To my parents and to my wife.

vi

Acknowledgements

First of all, I would like to thank my academic advisors, Profs. Henry Kapteyn
and Margaret Murnane for teaching me the experimental skills from scratch and forgiving me the freedom to explore the topics that interested me. Without their patient
guidance and generous support, this dissertation would not have been possible.
I would like to thank my close collaborators in the lab, Robynne Lock, Dr. Wen
Li, Dr. Nicholas Wagner, and Dr. Andrea Wüest for their inspiring discussions andhard work during the last three years I worked on the molecular HHG project.
I would also like to thank many people in Kapteyn-Murnane group who havetaught me so much about lasers, optics, computer programming and of course, physics
at various stages of my graduate school career. These include Xiaoshi Zhang, Tenio
Popmintchev, Daisy Raymondson, David Gaudiosi, Ariel Paul, Luis Miaja Avila, Oren
Cohen, Amy Lytle, Etienne Gagnon, Mark Siemens, Paul Alphin, Qing Li , Ming-chan
Chen and Jing Yin. I always appreciate the interactions and discussions with all themembers of KM group.
Helpful discussions and collaborations with people outside the KM group and
JILA, especially many theorists, are appreciated as well. Special thanks goes to Zach
Walter, Drs. Chris Greene, Ramakrishna Shankar, Tamar Seideman, An-Thu Le, ChiiDong Lin, Xinhua Xie, and Olga Smirnova, Serguei Patchkovskii and Albert Stolow.
I would like to thank the staffs at the JILA machine shop, electronic shop andcomputing facility for the help they gave me.

vii
Finally I would like to thank my wife, Jianying, for all the caring and love during
the last six years. The encouragement and love from her have always kept me cheerful,even when my experiments are not working as planned. She has also helped me discoverinterest outside physics and the lab.

viii

Contents

Chapter
1 Introduction1

1.1

Laser spectroscopy: an overview . . . . . . . . . . . . . . . . . . . . . .

1

1.2

Strong field spectroscopy of molecules . . . . . . . . . . . . . . . . . . .

3

1.3

Outline of this dissertation

5. . . . . . . . . . . . . . . . . . . . . . . . .

2 Theory of High-Order Harmonic Generation—The three-step model
2.1

7

Three step model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

10

2.1.1

Ionization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

10

2.1.2

Acceleration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

15

2.1.3

Recombination . . . . . . . . . . . . . . . . . . . . . . . . . . . .

16

2.2

The Lewenstein model and strong field approximation . . . . . . . . . .

17

2.3

Applications of HHG and propagation effects . . . . . . . . . . . . . . .

20

3 High-Order Harmonic Generation from Molecules—Experiments and Theoretical
Models24

3.1

Experimental Method . . . . . . . . . . . . . . . . . . . . . . . . . . . .

27

3.1.1

Laser system . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

27

3.1.2

Generation chamber and gas injection . . . . . . . . . . . . . . .

31

3.1.3

Imaging of the focus . . . . . . . . . . . . . . . . . . . . . . . . .

33

3.1.4

Detection of the HHG light . . . . . . . . . . . . . . . . . . . . .

34

ix
3.1.5
3.2

3.3

3.4

Data acquisition and analysis . . . . . . . . . . . . . . . . . . . .

34

Nonadiabatic molecular alignment . . . . . . . . . . . . . . . . . . . . .

36

3.2.1

The interaction Hamiltonian . . . . . . . . . . . . . . . . . . . .

36

3.2.2

Solving the TDSE . . . . . . . . . . . . . . . . . . . . . . . . . .

38

3.2.3

The expectation value and thermal averaging over initial states .

39

3.2.4

Periodical revivals after time zero . . . . . . . . . . . . . . . . . .

39

HHG from aligned molecules . . . . . . . . . . . . . . . . . . . . . . . .

42

3.3.1

Coherent buildup of HHG . . . . . . . . . . . . . . . . . . . . . .

42

3.3.2

Tomography of the molecular orbital . . . . . . . . . . . . . . . .

43

Recent theoretical advances . . . . . . . . . . . . . . . . . . . . . . . . .

46

3.4.1

Multielectron and multichannel ionization . . . . . . . . . . . . .

48

3.4.2

Recombination as an inverse process of photoionization . . . . .

49

4 Phase and Intensity Characterization of HHG Emission from Aligned Molecules 50
4.1

Two-center interference in molecular HHG . . . . . . . . . . . . . . . . .

50

4.2

Using gas mixtures to measure the phase of molecular HHG . . . . . . .

58

4.3

Double-focus interferometry for simultaneous intensity and phase measurement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

59

4.4

Quantum interference in CO2 molecules . . . . . . . . . . . . . . . . . .

61

4.5

Quantum interference in N2 O and N2 molecules . . . . . . . . . . . . . .

69

5 Polarization resolved characterization of HHG from aligned molecules
5.1

74

Observation of elliptically polarized HHG from molecules driven by linearly polarized laser light . . . . . . . . . . . . . . . . . . . . . . . . . .

74

5.1.1

Experimental setup . . . . . . . . . . . . . . . . . . . . . . . . . .

77

5.1.2

Intensity ratio between the parallel and perpendicular components 79

5.1.3

Orientation angle . . . . . . . . . . . . . . . . . . . . . . . . . . .

81

5.1.4

Ellipticity and phase delay84. . . . . . . . . . . . . . . . . . . . .

x
5.2

Polarization-resolved characterization of HHG emission from aligned moleculeswith elliptical polarized fundamental light . . . . . . . . . . . . . . . . .

6 Real Time Monitoring of Molecular Dynamics with HHG

87
94

6.1

Vibration in N2 O4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

95

6.2

HHG probing of N2 O4 dynamics . . . . . . . . . . . . . . . . . . . . . .

98

6.3

Monitoring the ionization yield . . . . . . . . . . . . . . . . . . . . . . . 100

6.4

Ruling out NO2 participation by interferometric measurement of thephase change in HHG from vibrating N2 O4 . . . . . . . . . . . . . . . . 104

6.5

Theoretical calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105

6.6

Saturation due to the depletion of ground state . . . . . . . . . . . . . . 108

6.7

Origins of HHG suppression at the inner turning point . . . . . . . . . . 111

6.8

Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

7 Summary and Future directions

115

7.1

Advantages and disadvantages of HHG spectroscopy . . . . . . . . . . . 115

7.2

Future directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116

118

Bibliography

Appendix
A Positive Dispersion Cavity Dump Ti: Sapphire Oscillator

127

A.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
A.2 Laser setup and performance . . . . . . . . . . . . . . . . . . . . . . . . 129
A.3 Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137

xi

TablesTable
3.1

The HOMO symmetry, ionization energy, and bond length for several
linear diatomic and triatomic molecules used in this work. . . . . . . . .

3.2

26

The rotational constant, rotational period, and anisotropic polarizability
for several common molecules . . . . . . . . . . . . . . . . . . . . . . . .

37

xii

FiguresFigure2.1

Time-dependent wave function evolution of a hydrogen atom in a strong
infrared laser field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

9

2.2Classical three-step model . . . . . . . . . . . . . . . . . . . . . . . . . .

11

2.3

Schematics of multiphoton, tunnel and above barrier ionizations

13

2.4

The dependence of the Keldysh parameter on the intensity and frequency. . . .

of the ionization laser radiation . . . . . . . . . . . . . . . . . . . . . . .

14

2.5

Classical calculation of the trajectory of the ionized electron in laser field

16

2.6

Typical HHG in time and frequency domains . . . . . . . . . . . . . . .

17

3.1

HOMO electron wave function for several linear diatomic and triatomic
molecules used in this work . . . . . . . . . . . . . . . . . . . . . . . . .

3.2

25

The experimental apparatus consists of four major components: a Ti:sapphire
amplifier, a Mach-Zehnder interferometer, a harmonic generation chamber, and a glancing-incidence EUV spectrometer. . . . . . . . . . . . . .

28

3.3

Typical spectrum and FROG trace of the amplifier output . . . . . . . .

30

3.4

HHG generation chamber . . . . . . . . . . . . . . . . . . . . . . . . . .

32

3.5

A typical image and fully vertical binned spectrum of the HHG in CO2

3.6

taken by the CCD camera, and transmission of 200 nm aluminum filter

35

Full rotational period of CO2 . . . . . . . . . . . . . . . . . . . . . . . .

40

xiii
3.7

Full rotational period of N2 . . . . . . . . . . . . . . . . . . . . . . . . .

3.8The schematics for tunnel ionization from HOMO to cation ground stateand from HOMO-1 to cation excited state. . . . . . . . . . . . . . . . . .

4.1

4.3
4.4

47

Illustration of the recolliding electron plane wave and the quantum interference of HHG in CO2 molecules . . . . . . . . . . . . . . . . . . . . . .

4.2

41

52

The evolution of HHG during a full rotational period of CO2 for harmonicorder 23, 33, and 37 with the alignment parameter cos2 θ . . . . . . . 53√
kR cos θ
The prefacter 2 sin(
) from two-center interference for CO2 molecules. 55
2
Schematic setup for directly measuring the intensity and phase of highharmonic emission from molecules. HHG from aligned and randomly
oriented molecules from two different regions interfere in the far field . .

4.5

60

Experimentally measured intensity (from the aligned molecular sample
only) for harmonic orders 19 - 45 as a function of time-delay between thealigning laser pulse and harmonic-generating pulse within the 3/4 revival

4.6

Lineout of harmonic orders 21, 25, 31, 35, 37, and 39 that exhibit different
sub-structure in the harmonic emission at optimal alignment . . . . . .

4.7

62

64

Interference pattern as a function of time within the 3/4 revival for harmonic orders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

65

4.8

Extracted value ofRversus harmonic order from the fits . . . . . . . .
λ

67

4.9

Measured harmonic intensity during a full rotational period of N2 O . . .

70

4.10 Interference pattern as a function of time delay for the 25th and 29th
harmonics for N2 O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

71

4.11 Intensity change versus time delay during a full rotational period of N2 .

73

5.1

Polarization schematic of high harmonic generation from aligned N2 . .

76

5.2

Setup for measure the polarization of HHG from aligned molecules andthe reflectivity of gold mirror for S and P polarized light. . . . . . . .

78

xiv
5.3

Ratio between the perpendicular (x) and parallel (y) components of the
HHG field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5.4

80

The temporal evolution of the perpendicular HHG component during afull rotational period of N2. . . . . . . . . . . . . . . . . . . . . . . . .

82

5.5

Interpolated color map of the orientation angle . . . . . . . . . . . . . .

83

5.6

Ellipticity ǫ for relative angles between the pump and probe and calculated phase difference δ between the parallel and perpendicular components of HHG emission in N2 . . . . . . . . . . . . . . . . . . . . . . . . .

5.7

Perpendicular HHG components from Ar atoms versus the fundamental
ellipticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5.8

90

Parallel HHG components from aligned N2 molecules versus the fundamental ellipticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5.9

85

91

Color map of perpendicular HHG component of 21st harmonic from N2
molecules as a function of the fundamental laser ellipticity and molecularalignment angle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

92

6.1

Setup and schematic of the N2 O4 experiment . . . . . . . . . . . . . . .

99

6.2

Harmonic yield vs. pump-probe delay using (A) parallel (k) and (B)perpendicular (⊥) pump and probe polarizations . . . . . . . . . . . . . 101

6.3

Time-dependent O+ yield from N2 O4 after strong field ionization.

6.4

Interference pattern obtained by combining HHG emission (15th order)
from vibrationally excited and unexcited N2 O4 .

. . . 103

. . . . . . . . . . . . . 106

6.5

Quantum chemistry calculation of neutral and cation state of N2 O4 . . . 109

6.6

Dyson orbitals and recombination dipoles corresponding to ionizing to
the Ag cation state and the B2g cation state. . . . . . . . . . . . . . . . 110

6.7

Laser intensity dependence of the vibrational modulation depth for different harmonics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

xv
A.1 The setup of the positive dispersion cavity dump oscillator . . . . . . . . 130
A.2 Spectrum from the cavity-dumped laser in the positive dispersion regime
with 6.5 W pump, with the dumper on and off . . . . . . . . . . . . . . 132
A.3 Typical microwave spectrum of the intra-cavity modulated pulse train . 133
A.4 Pulse energy, and average power as a function of dumping rate in the
PDR, with 6.5 W pump power . . . . . . . . . . . . . . . . . . . . . . . 135
A.5 Spectral (a) and time domain (b) profile of prism-recompressed pulse,
reconstructed from FROG measurement . . . . . . . . . . . . . . . . . . 136
A.6 Spectrum of the filament-induced white light. Inset: A digital photographof the generated white light continuum . . . . . . . . . . . . . . . . . . . 138

Chapter 1

Introduction

1.1

Laser spectroscopy: an overview
Linear and nonlinear laser optical spectroscopies of gas phase atoms and moleculesin the perturbative regime have become major tools for understanding the light-matterinteraction [1, 2]. What we have learned from the optical spectroscopy experiments iscentral to the understanding of quantum mechanics and its application in a multitude
of areas in physics and chemistry.
The instruments for a typical laser spectroscopy experiment are usually made upof three major components.
• One or more laser sources at varying wavelengths, intensities, and pulse durations.
• A gas-phase sample that is prepared and injected into an interaction chamber.
• A detection system for detecting the products of the light-matter interaction,
which consists of the detection of photons and/or particles resulting from ionization or fragmentation. A spectrometer and photon detector system can measure the intensity and wavelength of the transmitted and scattered light andthe spontaneous fluorescence after excitation. The electrons and charged ions
resulting from the fragmentation of the atoms or molecules can be detected byan energy resolved time-of-flight mass spectrometer.

2
While breakthroughs in each of these three component technologies contributes
to the progress of laser spectroscopy, the most important component may be the development of new laser sources. Early laser optical spectroscopy techniques—such as absorption spectroscopy and laser induced fluorescence at difference wavelengths—mainly
investigated the bound-bound transition between the electronic, vibrational, and rotational states. Recently pushing the spectral line measurement to higher resolution has
initiated a number of breakthroughs in physics, such as the realization of Bose-Einsteincondensation in dilute atomic gases [3] and the discovery of frequency comb techniques[4].
Ionization spectroscopy [2], especially photoelectron spectroscopy with high energy photons (UV, VUV, EUV and Soft X ray) and resonance enhanced multiphoton
ionization (REMPI) allow the investigation of the bound-continuum transition. Compared to high energy photons, REMPI is state selective, thus the state distributionof the molecular fragment offers interesting information about the molecular process.
These techniques have become available in many physical chemistry laboratories.
With the development of short pulse laser technologies, such as cavity dumping
and Q-switching, nanosecond pulsed lasers with 106 W/cm2 focused intensity become
possible. Rich nonlinear optical phenomena come into play at this intensity, including
nonlinear harmonic generation and coherent Raman scattering.
Passive mode locking techniques [5], first invented using dye laser (colliding pulse
mode locking), then advancing to solid state Ti: Sapphire laser (Kerr lens mode locking).
This progress has pushed the pulse duration to picosecond (ps) and femtosecond (fs).
Using the femtosecond lasers, ultrafast spectroscopy employing pump-probe techniques
enables real time monitoring of molecular dynamics [6]. For the first time, the time
evolution of rotational and vibrational dynamics of molecules could be observed in time
domain and compared to theoretical calculations. Although time-domain techniques
trade off time resolution at the expense of spectral resolution, a good understanding

3of wave packet motion formed by the superposition of a large number of states hasoffered a playground for studying and controlling atom motion in molecules [7]. By
combining high power Ti: Sapphire laser and nonlinear optical frequency conversion
techniques, such as harmonic generation in crystal and gases and optical parametricamplification, it becomes possible to generate an ultrafast rainbow covering from theultraviolet (UV) to the infrared (IR), and this source can readily be used to explore
molecular physics and chemistry. Combination of new pump-probe technique with traditional laser spectroscopy technique, results in techniques such as transient absorption,
femtosecond photoelectron spectroscopy, Raman spectroscopy, etc..
In addition to advances in laser development, gas sample preparation techniques
have also made considerable progress. Molecular motion can be slowed down by the
adiabatic expansion in a supersonic molecular beam, which enhances the resolution of
the energy and momentum resolved spectroscopy. Experimental detection methods havealso been improved. Photon counting makes it possible to observe new phenomena atsingle photon level, while charged coupled device (CCD) cameras sensitive to various
wavelength light can collect data with very low noise level [8]. On the charged particle
side, angular resolved photoion and photoelectron imaging and coincidence techniques
can retrieve the 3D vector momentum of the charged particle from a specific reaction
channel and offer more detailed information about molecular fragmentations and reactions [9, 10].

1.2

Strong field spectroscopy of molecules
In all of the spectroscopy techniques mentioned above, the interaction between

the atomic or molecular electron and the external light field is considerably weaker
than the Coulomb binding force between the nucleus and the electron; i.e. the electron
wave function is only slightly reshaped by the external field. Theoretically, the laser

4
atom interaction can be treated as a perturbation to the field free atomic or molecular
Hamiltonian.
State-of-the-art ultrashort pulse lasers offer not only higher temporal resolution,
but also the possibility to generate more intense light. Chirp pulse amplification techniques have advanced to the point that sub-50fs pulses with 1012 to 1016 W/cm2 intensity
can routinely be generated by table-top lasers at high repetition rate. The electric fieldat the focus is comparable to the binding electric field between the nucleus and the electrons. For the hydrogen atom, the binding electric field is 5.2×109 V/m (corresponding
to an intensity of 3.5×1016 W/cm2 ).
In this intensity regime, a fascinating phenomenon is the high-order harmonic
generation (HHG) process, In HHG, by focusing a Ti: Sapphire laser at a center wavelength of 790nm (photon energy 1.56 eV) into a gas sample, we can generate a frequency
comb at the odd-order frequencies of the fundamental laser light. The centrosymmetryof the gas medium prevents the generation of even-order harmonics. Unlike in the perturbative regime where the harmonics decrease exponentially with the harmonic order,
the plateau region high harmonics in this intensity regime can span a few hundred eVin energy and can extend to the keV range [11].
The work in this dissertation includes studying the HHG from an aligned or excited molecular sample. On one hand, we demonstrate that information about molecular
structure and dynamics can be encoded on the various properties of the HHG, such as
intensity, phase, and polarization. These data have broad implications for the theory ofmolecules in strong fields because they cannot be explained by simple theories based onstrong field approximation (SFA) and single active electron approximation (SAEA). On
the other hand, when combined with the intrinsic temporal resolution of HHG, simultaneous measurements of structure and dynamics are possible. This shows possibilityof making a molecular movie with HHG during during a fast reaction process.

5

1.3

Outline of this dissertation
This dissertation is organized as follows:
In Chapter 2, we review the theoretical and experimental background of HHG

generation in atoms. To model the HHG from single atoms, two methods can be used,
the time-dependent Schrödinger equation and the semiclassical three step model [12,13, 14]. Much of our insight about the HHG process was gained from the classical threestep model and its quantum mechanical correspondence, the Lewenstein model.
In Chapter 3, we discuss the motivation to study HHG from molecules and introduce the theoretical and experimental background of HHG generation in molecules.
We also review previous experiments that initiate the efforts to develop HHG as aspectroscopy tool for molecules.
Chapter 4 presents experimental work on the measurement of the intensity andphase of HHG emission from transiently aligned molecules. Experimental results on
three simple molecules N2 , CO2 and N2 O are presented and compared with a two-chargecenter quantum interference model which is based on a plane wave approximation of
the recolliding electron. The data on CO2 and N2 O molecules can be explained well by
the two-charge-center model. However, this simple model does not work very well forN2 molecules.
Chapter 5 presents two experiments. First, we perform an accurate polarimetry
measurement of high harmonic emission from aligned molecules. We find that harmonic
emission from nitrogen molecules can be strongly elliptically polarized; even when driven
by linearly polarized laser fields. Furthermore, we extract the relative phase difference
between the parallel and perpendicular components of the high harmonic field, whichstrongly depends on the harmonic order. This work also shows that it is possible
to engineer the polarization properties of harmonic emission by carefully preparing amolecular medium. In the second experiment, we vary the ellipticity of the driving laser

6
used to generate the high harmonic emission. We find that the HHG intensity fromaligned molecules does not optimize with linear polarization of the driving laser (as in
the atomic case), but rather peaks at a small positive or negative ellipticity. The signand degree of this ellipticity depend on the molecular orientation.
In Chapter 6, we investigate the HHG from vibrating N2 O4 molecules. We showthat the intrinsic properties of HHG make it a very promising tool for time resolved
measurement of molecular dynamics. However, due to the complexity of this process,to make further progress, it will be very important to develop and test new theories
beyond the strong field approximation.
In chapter 7, we summarize the results and point to future directions.
In the appendix, we present another experiment conducted earlier, and indirectly
related to the main line of this dissertation. In this experiment, We demonstrate forthe first time that 0.45 µJ pulses can be obtained from a cavity-dumped Ti: Sapphireoscillator stably operating in the positive dispersion regime. The output pulse canbe compressed to 60 fs and used to generate a white light continuum through selffilamentation in a thin sapphire plate.

Chapter 2Theory of High-Order Harmonic Generation—The three-step model

In the laser intensity range of 1013 to 1016 W/cm2 , the strong field atomic andmolecular phenomena result from the extreme distortion of the electronic wave functionof an atom or molecule in the presence of the laser electric field.
To deal with the strong field response of atoms and molecules in general, and
HHG in particular, the most rigorous, but computationally-demanding method is the
direct integration of the time-dependent Schrödinger equation (TDSE):∂ψ(r, t)1h̄2 2=
∇ + V (r, t) ψ(r, t),
−
∂t
ih̄
2m
#

"

(2.1)

where the time-dependent potential V (r, t) is the sum of the atomic potential Vatomic (r)and the dipole interaction with the laser electric field er · E(t) [15, 16], where E(t) =êEcos(ωt + ψ) is the oscillating electric field vector of the laser. The exact solution ofthis equation can be written in integral form,(Z
tfψ(r, tf ) = e

ti

h̄2 2
dt
−
∇ + V (r, t)
ih̄
2m
"

#)

ψ(r, ti ),(2.2)

where ti and tf are the initial and final time.
To solve this equation numerically, we split the operator with a small time step ∆tto eliminate the time dependence of potential during each time step. We then integrateby parts,
ψ(r, tf )

= exp

"
(N −1
X ∆t

h̄2 2
−
∇ + V (r, n∆t)
ih̄
2m
n=0

#)

ψ(r, ti )

8
=

(N −1
Y
n=0

exp

(

∆t
h̄2 2
∇ + V (r, n∆t)
−
ih̄
2m

#))

"

ψ(r, ti ),(2.3)

Using the identity of the Fourier transform, we obtain
n

e

∆t
ih̄

h

2

h̄
− 2m
∇2 +V (r,t+∆t)ioψ(r, t)

=F
=F

−1
−1

n

Fe


∆t
ih̄

h

2

h̄
− 2m
∇2 +V (r,t+∆t)
2

p
− ∆t
ih̄ 2meF e∆tV (r,t+∆t)ih̄

ioψ(r, t)ψ(r, t). (2.4)In this way, the propagation of the wave function in time can be calculated by theiterative Fourier transform between real and momentum spaces. If the temporal step
length and spatial grid size are small enough, the numerical solution of the TDSE canbe very accurate.
Once the time-dependent electronic wave function is known, the power spectrumof HHG can be calculated through the Fourier transform of the dipole acceleration(second order derivative of the time-dependent dipole moment). The calculation of the
HHG amplitude in the length, velocity and acceleration gauges is shown in Eqn. 2.5.

S(Ω)

(

)

d2
hψ(r, t) |r| ψ(r, t)i = Ω4 F {hψ(r, t) |r| ψ(r, t)i}
=F
dt2


d
=F
hψ(r, t) |v| ψ(r, t)i = Ω2 F {hψ(r, t) |v| ψ(r, t)i}dt
= F {hψ(r, t) |a| ψ(r, t)i}

(2.5)

As an example, the wave function evolution of a hydrogen atom in a strong laser
field is shown in Fig. 2.1. An 800 nm laser pulse with a peak focused intensity of
3×1014 W/cm2 is used in the 2-dimensional TDSE calculation. In principle, given the
wave function ψ(r, t) solved using the TDSE, these three gauges should give the same
results. However, if approximations are used when the wave function is solved, theresult will depend on the gauge used.
Although the TDSE can be solved in the case hydrogen atom, it requires considerable computational time. Even for helium atoms or hydrogen molecular ions, a9Figure 2.1: This figure shows how the wave function of a hydrogen atom evolves withtime in a strong infrared laser field. Before the pulse arrives, the wave function is
localized or bound. As the electric field becomes stronger, the electron density starts
to tunnel through the barrier and to spread in space. The oscillation of the electron
density shows the wave nature of the electron.

10
full calculation (including three spatial dimensions and the temporal dimension) is still
considered state-of-the-art. Thus the TDSE is intractable for multielectron atoms. To
simulate multielectron atoms with TDSE, we can consider a single active electron underan effective Hartree-Fock potential. Calculations have been carried out for Xe and Ne
atoms [15, 16].

2.1

Three step model
For more complex atoms or molecules, it is harder to construct a potential function

to exactly simulate the energy and wave function of electrons. Fortunately, a simple
semiclassical three-step model [12, 13, 14] can be used to understand much of the physics
of the HHG process. As we show, the three-step model and its variations offer more
physical insights than solving the TDSE directly. In the three-step model of HHG, theelectric field of a focused laser first ionizes an outer valence electron from the groundstate of an atom or molecule. This electron is then accelerated by the electric field of
the laser. If it returns to the vicinity of the parent ion, the electron can recombine into
the ground state. This continuum-bound transition converts the kinetic energy of theelectron into an extreme ultraviolet (EUV) photon.

2.1.1

Ionization

In the intensity regime above 1014 W/cm2 , ionization is the dominant process
and the starting point for consequent physical processes. In 1965, Keldysh published aclassical paper [17], where he gave a unified picture of nonlinear ionization by both low
and high frequency lasers. The Keldysh theory identifies two limiting cases of strong
field ionization— tunnel and multiphoton ionization—distinguished by the so-called
Keldysh adiabatic parameter. The Keldysh parameter depends on three quantities: theionization potential Ip of the atom, the laser frequency ω, and the electric field strength

R

ec

ol

lis

io

n

11

EUV photon

Acceleration

Ionization

Figure 2.2: Schematic of the classical three-step model of HHG, including ionization,
acceleration, and recollision steps.

12
E. The Keldysh parameter can be defined ass√
ω 2mIP
2Ip
Ttunnel
γ=
=
=
,
eE
Up
Toptical(2.6)

e2 E 2is the average kinetic
4mω 2
p
2me Ipis theenergy of the electron in the oscillating electric field, and Tionization = 2πeEwhere e and m are the charge and mass of electron, Up =ionization time the electron takes to tunnel through the barrier.
At high laser frequency, when γ ≫ 1, multiphoton ionization, as shown in Fig.
2.3(a) is the dominant process. This process is well described by perturbation theory.
The ionization rate is proportional to E 2q , where q is the order of the nonlinear process.
In the multiphoton ionization regime, there is insufficient time for the electron to tunnel
through the barrier during each laser cycle. The electron is bounced back and forth by
the oscillating potential until it absorbs enough photons to become a free electron.
For ω → 0, γ ≪ 1 and Ttunnel ≪ Toptical , the ionization can be seen as quasistatic. The electron has enough time to tunnel through the barrier in one laser cycle,
as shown in Fig. 2.3(b). This is called the tunnelling limit.
For certain atomic species, the Keldysh parameter depends on both the strengthof the electric field and the frequency of the laser, which is plotted in Fig. 2.4. We cansee that, at the intensity of 1014 W/cm2 , the Keldysh parameter is around 1. Thus weare in the intermediate region between tunnel and multiphoton ionization.
When the electric field becomes even stronger, the maximum of the potential
barrier becomes significantly lower than Ip , and the ionization becomes above-barrier
as shown in Fig.

2.3 (c).

Above-barrier ionization for hydrogen atoms occurs at

1.5×1014 W/cm2 , according to simple calculations. The practical threshold for abovebarrier ionization is usually higher than this value due to quantum mechanical effects.
The Keldysh theory was generalized to calculate the tunnel ionization probabilityof an arbitrary electronic state of an atom or ion in 1986 (the ADK theory) [18],w(t) = An∗ l∗ Bl,|m| Ip (2(2Ip )3/2 2n∗ −|m|−12(2Ip )3/2
)
exp(−
)
E(t)
3E(t)

13

(a)

Multi-photon ionization(b)

Potential Energy [eV]
10

-15

-10

-5

5

10

15

10

15

Distance [Angstrom]

-10

-20

-30

Tunnel ionization(c)Potential Energy [eV]10Distance [Angstrom]
-15

-10

-5

5
-10

-20

-30

Above barrier ionization

Figure 2.3: (a) In the multiphoton ionization regime, there is insufficient time forthe electron to tunnel through the barrier during each laser cycle, and the electron
is bounced back and forth by the time-dependent potential. (b) and (c) While in thetunnel and above-barrier regime, ionization can be considered as quasistatic.

14

Figure 2.4: The dependence of the Keldysh parameter on the intensity and frequencyof the ionization laser radiation.

15
where E(t) is the instantaneous electric field amplitude, Ip is t the ionization potential
and
∗

22n
An∗ l∗ = ∗n Γ(n∗ + l∗ + 1)Γ(n∗ − l∗ )andBl,|m| =(2l + 1)(l + |m|)!
2|m| |m|!(l − |m|)!

are defined by the angular quantum number l and the magnetic quantum number m ofthe electron. We can calculate the total ionization rate by integrating the instantaneous
ionization probability over the laser pulse duration. ADK theory has been shown to berelatively accurate for calculating the instantaneous ionization rate for noble gases inthe γ ≈ 1 regime.
2.1.2

Acceleration

After ionization, the electron oscillates in the electric field under the influence ofCoulomb forces of the nucleus. In the strong field and low frequency regime, the effectof the nuclear Coulomb force on the ionized electron can be neglected; this is referred
to as the strong field approximation (SFA). Depending on the phase in the laser cyclethat the electron is ionized, it is possible that the electron will reverse its direction
and return to the core. A simple calculation shows that for a cos(ωt) waveform, theelectron ionized in the phase regime [0,π/2] and [π,3π/2] will return to the core, while
the electron ionized at any other phases of the cycle will not return. The electrons
ionized at ≈ π/10 after the field peak will gain the maximum kinetic energy 3.2Up when
it returns to the core. We plot the return time and return kinetic energy for electrons
ionized at different phases of the laser cycle in Fig. 2.5. As we can see from Fig. 2.5, if
the return kinetic energy of the electron is less than 3.2Up , two electron trajectories will
be associated with this kinetic energy. For the long trajectory the electron is ionized
before π/10 and spends more time in the continuum. For the short trajectory, the16electron is ionized after π/10 and spends less time in the continuum.
Return Kinetic Energy

Return Time
6

20

Return Kinetic Energy (eV)Return time (fs)

5

4

3

2

1
0

0.5

1
1.5
Ionization phase (Rad)

2

15

10

5

0
0

0.5

1
1.5
Ionization phase (Rad)2

Figure 2.5: The classical calculation of return time and kinetic energy of the electrons
ionized at different phases of a laser pulse with intensity of 1014 W/cm2 .

2.1.3

Recombination

Recombination of the photoelectron to the parent ion will generate one highenergy photon. The frequencies of the generated photons correspond to odd-order harmonics of the incident laser light. The maximum kinetic energy Ip +3.2 Up of the return
electron defines the cutoff energy of HHG as shown in Fig. 2.6, which agrees surprisingly
well with the experimental result of HHG from noble gases [19].
The three-step model can also explain other processes in the strong laser fields.
The elastic scattering of electrons will contribute to the process referred to as high-order
above-threshold ionization (ATI), because more photons than necessary are absorbed
to ionize the electron, and the extra photons are converted into kinetic energy of theelectron. In the last process, non-sequential double ionization (NSDI), the inelastic
recollision of the photoelectron to the parent ion will kick out another electron andgenerate a doubly charged ion.

Time domain

17Frequency domain
perturbative
plateau
cut-off

2.7fs

Temporal cycles of 800 nm laser

Harmonic orderFigure 2.6: Typical HHG in time and frequency domains.

2.2

The Lewenstein model and strong field approximation
An elegant semiclassical quantum model of HHG has been developed in which

the classical model has been embedded [10]. For the linearly polarized monochromatic
light, the Hamiltonian in the length gauge can be written as H = H0 (t) + VL (t) =H0 + xE cos ωt, assuming x̂ is the polarization direction (note that we use atomic units(e = m = h̄ = 1) throughout this section). An exact solution of this equation can be
written as
Rt|ψ(t)i = −i 0 dτ



−i

e

Rt
τ

Ĥ(t′ )dt′

Rt





−i

VL (τ ) e′′+e−i 0 Ĥ0 (t )dt |gi .

Rτ
0Ĥ0 (t′ )dt′



|gi



(2.7)

Assuming H0 is the field-free Hamiltonian, and plugging in H0 |gi = −Ip |gi, we obtain|ψ(t)i = −i

Z t
0

dτ



Rt

′

′



h

i



−i(−Ip t)e−i τ Ĥ(t )dt VL (τ ) e−i(−Ip τ ) |gi + ee

|gi .

(2.8)

A natural explanation of this expression is that the electron is ionized at time τ . Before
this time the electron evolved in the ground state; after that time the motion of theelectron is governed by the total Hamiltonian. With the following two assumptions(1) All atomic states except the ground state and continuum states labeled by the
momentum |vi are ignored.

18(2) The depletion of the ground state is neglected.
The continuum part of the wave function can be expanded with the free electron wave
function,+iIp t|ψ(t)i = e

|gi +

Z

d3 vb(v, t) |vi ,where the expansion coefficient b(v, t) can be given byb(v, t) = hv |ψ(t)i = −i
Rt

′

Z t
0





Rt

′

′



i

h



dτ hv| e−i τ Ĥ(t )dt VL (τ ) e−i(−Ip τ ) |gi .
Rt

′

′

′

Under SFA, e−i τ Ĥ(t )dt can be replaced by e−i τ ĤF (t )dt . The free electron
Volkov propagator then becomes
Rt

′

Rt

′

′

′

Rt

′

′

hv| e−i τ Ĥ(t )dt = hv| e−i τ ĤF (t )dt = hv| ei τ ĤF (t )dti= hv(τ )| eRtτKE(t′ )dt′

−i

=e

Rt
τ

KE(t′ )dt′hv(τ )|(2.9)

Thus the expansion coefficient b(v, t) can be given by
hv |ψ(t)i = −i

Z t



−i

dτ e

0

Rt
τ

KE(t′ )dt′

+iIp τ

hv(τ )| VL (τ ) |gi e(2.10)

where KE(t) is the free electron kinetic energy.
According to the dipole approximation E(t) = −∂A(t), the momentum change∂tof the electron in the electric field isZ tτ

eE(t)dt′ = −

Z t
τ

e

∂A(t) ′
dt = −e [A(t) − A(τ )] = m(v − v(τ )).
∂t

We can now introduce the new conserved quantity, canonical momentum
p = v + A(t) = v(τ ) + A(τ ).
So the electron kinetic energy can be expressed as
1
1
1
KE(t) = v(t)2 = (v(τ ) + A(τ ) − A(t))2 = (p − A(t))2 .
2
2
2

19
Plugging in VL (τ ) = xE cos(ωτ ), the wave function can be written as


Rt

′1

2

′

= −i 0t dτ E cos(ωτ ) e−i τ dt 2 [p−A(t )] hv(τ )| x |gi e+iIp τb(v(t), t)

R



Rt

′1

′





2

= −i 0t dτ E cos(ωτ ) e−i τ dt 2 [p−A(t )] dx (p − A(τ ))e+iIp τ ,R(2.11)

where dx (p − A(τ )) = hv(τ )| x |gi.
We then calculate the dipole moment by neglecting the continuum-continuum
transition

=i

Z t

x(t) = hψ(t)| x |ψ(t)i =
dτ

0

Z

Z

d3 vd∗x (v)b(v, t) + c.c.

d3 pE cos(ωτ )d∗x (p − A(t))e−iS(p,t,τ ) dx (p − A(τ )) + c.c.

where the classical action S(p, t, τ ) is defined as

Rt

′
τ dt

n

1
′ 2
2 [p − A(t )] + Ip

(2.12)o. The dipole

term dx (p − A(τ )) describes the transition between the ground state and continuum
state at ionization. The dipole term d∗x (p − A(t)) is the recombination dipole between
the continuum state and the ground state. Then e−iS(p,t,τ ) gives the phase accumulatedby the electron when it is accelerated in the continuum, which is referred to as theintrinsic phase of the HHG.
The Fourier transform of the dipole acceleration is the amplitude of the HHG:
S(Ω = qω) =Zẍ(t)e−iΩt dt = −Ω2Zx(t)e−iΩt dt

Due to the sinusoidal oscillation of the electric field and the central symmetry of theatomic potential, x(t) can be expanded a as Fourier series, x(t) =P
Kwith the coefficients defined asZ 2πdtx(t)ei(2K+1)ωtdtdτx2K+1 ==i

Z 2π
0x2K+1 ei(2K+1)ωt ,

0

Z t
0

Z

d3 pE cos(ωτ )d∗x (p − A(t))e−iS(p,t,τ )+(2K+1)iωt dx (p − A(τ ))+c.c.
Then [(2K + 1)ω]2 x2K+1 is the amplitude of the q = (2K + 1) order harmonic.

(2.13)

20
This integral can be evaluated by the stationary phase (saddle point) approximation, and the stationary phase conditions for each of these three integrals are shown
below,(1) For p , ∇p S(p, t, τ ) = x(t) − x(τ ) = 0∂S(p, t, τ )∂(2) For τ ,
=
∂τ
∂τ

Z t

dt

τ

0
(3) For t ,

′



2
1
p − A(t′ ) + Ip
2



=

1
[p(τ )−A(τ )]2 + Ip =2

∂S(p, t, τ )1
1= [p − A(t)]2 − [p − A(τ )]2 + Ip = (2K + 1)ω
∂t2
2These three conditions correspond elegantly to the assumptions made in the classical method. Condition (1) means that the electron should return to the vicinity of theparent ion. Condition (2) corresponds to the zero initial velocity after ionization, assuming 12 [p(τ )−A(τ )]2 = −Ip ≪ Up . Condition (3) is simply energy conservation. The
saddle point method reveals that the most important contribution to HHG is from the“quantum trajectories” which are close to the classical motion of the electron. This is a
result of the quantum interference of all quantum paths, and is similar to the Feynman
path integral.
Eqn. 2.12 can be easily generalized to a laser field with an arbitrary polarization
direction,
D(t) = hψ(t)| r |ψ(t)i =
=i

Z t
0

2.3

dτ

Z

Z

d3 vd∗x (v)b(v, t) + c.c.

d3 p cos(ωτ )d∗ (p − A(t))e−iS(p,t,τ ) [E · d(p − A(τ ))] + c.c. (2.14)

Applications of HHG and propagation effects
According to the thee-step model, the recollision process repeats each half laser

cycle, generating a burst of EUV radiation. In the time domain, this forms a pulse
train synchronized with the fundamental laser, as shown in Fig. 2.6. Since the EUV

21burst is confined to each half laser cycle, the pulse duration of each burst is in theattosecond regime. In the spectral domain, this corresponds to a comb with a spacing
twice the fundamental laser frequency. An intense IR pulse with a well controlled
waveform can confine the EUV radiation to only one half cycle, and thus is able togenerate a single attosecond pulse. This highly coherent radiation in the soft X-ray
spectrum with attosecond pulse structure has been recognized as an important tool fortime resolved spectroscopy. Both the single attosecond pulse generated with a few-cycle
IR pulse and the attosecond pulse train generated with a multi-cycle IR pulse have been
experimentally characterized and applied to a few proof of principle applications [20].
Even without the attosecond time resolution, HHG is still a very good universitylab-scale alternative to synchrotron sources. HHG sources are especially good for experiments which require short temporal resolution and modest pulse energy, such as
photoelectron spectroscopy of gases or solid surfaces.
The most important barrier for attosecond science as an emerging field is the low
flux that can be generated particularly at shorter wavelengths. To further enhance theconversion efficiency from fundamental laser to HHG, it is important to understand the
propagation of the fundamental laser and HHG in the generation medium, especially thephase mismatch ∆k = qkω − KΩ . Similar to the case of low order harmonic generation,
the phase velocity difference between HHG and the fundamental infrared light will
limit the effective interaction length to the coherence length Lc = π/∆k. Four terms
contribute to the phase mismatch ∆k,(1) The index of refraction difference between the fundamental laser and HHG ina neutral gas ∆k = −q

2π
(1 − η)(nq − n), where nq − n represents the index of
λ0

refraction difference between the qth harmonic and the fundamental laser, λ0 is
the wavelength of the fundamental laser, and η is the ionization level that canbe calculated by the ADK formula.

22(2) The index of refraction difference between fundamental laser and HHG in aplasma (free electron)Na ηe2 λ0 q 2 − 1, where Na is the density of the gas.
mc2q(3) The geometric phase of the fundamental laser due to the propagation or focusing geometry. For a free space focus, the Gouy phase shift can be written
as q arctan(z/b), where z is the longitudinal coordinate and b is the confocal
parameter. Since ∆Φ =R

R∆kdz = (KΩ − qkω )dz, the gradient of ∆Φ gives∆k. For a fiber, the geometric term is written as ∆k =2 λ q2 − 1Unm0, where2
4πaq

Unm is related to the propagation mode in the fiber. The q factor comes fromthe fact that the cycle time of the fundamental is q times the cycle time of the
HHG.
(4) The intensity dependent intrinsic phase, as we mentioned in our discussion of
the Lewenstein model. This term depends on the harmonic order and laser
intensity distribution.
The relative importance of these terms depends on the geometry of HHG. In thegas jet geometry, a Gaussian laser beam is focused into a thin gas jet. The intensity
dependent atomic phase and the Gouy phase are dominant terms. Since the intrinsic
phase of long and short trajectories differ in intensity dependence, the short trajectories
can only be phase-matched on axis when focused before the gas jet, while the long
trajectories can only be phase matched on axis when focused after the gas jet [21].
For harmonic generation in a fiber [22], there is no Gouy phase shift. Thus theindex of refraction difference between the fundamental and HHG in the neutral gas andelectron plasma are dominant terms. Tuning the gas pressure can fully phase-match arange of harmonics in a hollow fiber. This method offers more harmonic flux and better
coherence than the HHG produced from a gas jet. The spatial intensity distribution in
the transverse direction will confine the phase matching region to mainly near the axis,
thus reducing the HHG beam size. These properties make the HHG in a hollow fiber

23
available as a source for microscopy and high resolution imaging [23].

Chapter 3

High-Order Harmonic Generation from Molecules—Experiments andTheoretical Models

In contrast to atoms, molecules have more complicated electronic structure andinvolve rotational and vibrational freedom. Molecular orbital theory mathematicallydescribes the electronic wave function of a molecule by a superposition of atomic orbitals(basis sets). Sophisticated quantum chemistry code implements self-consistent fieldcalculations (methods) to calculate the coefficients of atomic orbital components.
These calculations can predict various properties of molecules, such as optimized
molecular geometry (bond length and bond angle), vibrational frequency, energy, wave
function, permanent dipole moment, and polarizability of certain electronic states. In
Fig. 3.1, we list electronic wave functions of the highest occupied molecular orbitals(HOMO) for several linear diatomic and triatomic molecules used in this work. Also intable 3.1, we list the HOMO symmetry, the ionization energy, and the bond length ofthese molecules. People generally rely on quantum chemistry calculations to understandthe structure and dynamics of small gas-phase molecules. The accuracy of the calculated
electronic wave function can be verified by indirect experimental measurements, suchas vibrational frequency and the energy level of electronic states. However a direct
measurement of the electron wave function is always preferable.
The density distributions of the electrons and the positions of the nuclei canbe obtained by hard X-ray diffraction [24]. However, large samples with crystallized25

H 2 σgO2 πgN 2 σgCO2 πgN2O πgFigure 3.1: HOMO electron wave function for several linear diatomic and triatomic
molecules used in this work. the Hartree-Fock single point energy calculation was donewith the 6-31G basis set.

26
structure are needed for these experiments. The X-ray pulse durations from synchrotron
sources are usually longer than a few ps, thus offering poor time resolution.
Table 3.1: The HOMO symmetry, ionization energy, and bond length for several linear
diatomic and triatomic molecules used in this work.
Molecule
H2
D2
O2
N2
CO2
N2 O

HOMO symmetry
σg
σg
πg
σg
πg
πg

Ip
15.43
15.47
12.03
15.58
13.78
12.89

Bond length
0.741 Å
0.742 Å
1.208 Å
1.098 ÅC-O:1.16 Å
N-N:1.186 Å
N-O: 1.126Å

Strong field processes such as ionization and HHG are assumed to be sensitive
to molecular structure, especially to the electron wave function of the HOMO. The
suppression of ionization in O2 molecules compared to Xe has been explained as theinterference of two electron sites [25]. By fitting the wave function of molecules in
the asymptotic area with a single center atomic wave function, ADK theory has been
generalized to molecules. With this theory, the angularly dependent ionization has been
predicted [26].
Since the development of molecular alignment techniques, there has been increased interest in studying high harmonic generation (HHG) from field-free rotationallyaligned molecules or vibrating molecules. Using a simple analogy, an atom or molecule
driven by a strong laser field behaves like an antenna—the radiated field will depend on
the shape of the antenna, which in the case of HHG is the shape and orientation of themolecular electronic wave function or molecular orbital. Thus important information
about the atoms and molecules is encoded on the properties of the HHG emission.
The motivation to study HHG from molecules is two-fold. Firstly, once we understand the HHG processes in molecules, coherent control of the generated EUV radiation
might become possible by manipulating molecular emitters. Secondly but more impor-27tantly, recent experiments (as reviewed later) enable the possibility of imaging molecular
structure and dynamics with HHG. Monitoring the structure change in real time offers
the opportunity to understand the correlation between structure and dynamics, since
the dynamics of the molecules is determined by their transient structure. The evolution
from unstable transient structure to stable structure is important to a chemical reaction. Thus the ability to record the electronic wave function changes during a chemical
reaction is valuable. HHG has the intrinsically short time resolution, and as will be
discussed in the following, it can offer certain structural information as well. These two
characteristics allow HHG to give structural and dynamical information simultaneously.
Recently developed time-resolved photoion-photoelectron spectroscopy and imaging techniques can monitor the electron or ion momentum in real time. Combining thesewith coincidence techniques, indirect structural information can be obtained [27]. Ultrafast electron diffraction (UED) is another promising direction for gas phase molecular
dynamics, but the time resolution is limited to the ps range due to the spatial charge
effect, which will stretch the duration of the electron pulse [28].

3.1

Experimental Method
In this section, I briefly review the experimental setup and methodology of themolecular HHG experiments. The experimental setup, which consists of a laser system,and harmonic generation and detection chambers, is shown in Fig. 3.2.

3.1.1

Laser system

The fundamental laser light for the HHG experiment is delivered by a high-average
power, 2-stage, 1 kHz repetition rate Ti:sapphire amplifier. A 100 MHz pulse train froma Kerr lens mode-locking Ti: sapphire oscillator is amplified, employing the principleof chirped pulse amplification [29, 30]. The energy of the pulse from the oscillator is

DAQ computer

300 µJ,25 fs

Gold coated grating

f=30 cm

800 nm laser, 2-4 mJ 25 fs

CCD
Al filter

300 µJ, 140 fs
HWP f=50 cm

Cylindrical mirror

Vacuum Chamber

Figure 3.2: The experimental apparatus consists of four major components: a Ti:sapphire amplifier, a Mach-Zehnder interferometer, aharmonic generation chamber, and a glancing-incidence EUV spectrometer.

28

29
about 3-5 nJ, with a transform-limited pulse duration less than 20 fs. In the first stageof the amplifier system, a grating-based stretcher stretches the pulse to 20 ps and a
Pockels cell can select a 1 kHz pulse train. After recollimation, the pulse is sent to themultipass amplification stage pumped by an intracavity doubled Nd:YAG laser (Falcon,
Quantronix, 20 mJ pulse energy, 100 ns pulse duration). After the first stage, the pulse
goes through another Pockels cell to supress the amplified stimulated emission. The
pulse is further amplified in a double-pass second stage. In both stages, the Ti:Sapphire
crystals are contained in cryostat vacuum cells. The copper crystal holders are cooled
down to 77 K using liquid nitrogen, cooling can reduce the thermal lens in the Ti:
sapphire crystals and improve the beam quality. To avoid water condensation on the
crystals, both the cells are maintained under high vacuum by an ion pump. Afterthe amplification, a compressor is used to recompress the pulse to nearly transform
limited pulse duration. This amplifier is capable of generating a 25-30fs pulse with morethan 5 mJ energy and a decent beam spatial profile (M 2 <1.5). We characterize thespatial profile and pulse duration using a beam profiler (Spiricon) and second harmonic
generation based frequency resolved optical gating (FROG). The typical spectrum and
FROG trace of the amplifier output are shown in Fig. 3.3.
A Mach-Zehnder type interferometer was used to implement the pump-probe
experiments. We split the output pulse from the amplifier to pump and probe beams
by a dielectric beam splitter. We vary the transmission of this beam splitter from
20% to 40%, depending on the experimental requirements. A computer-controlled,
motorized translation stage is used to adjust the delay between the pump and probe
beams. The energies, pulse durations and polarizations of the pump and probe pulses
can be separately controlled by adding various optics, such as a wave plate or polarizer
into the beam paths of pump and probe. The pump and probe pulses are focused by
two anti-reflection coated lenses and recombined either collinearly or non-collinearly
before the vacuum chamber The lenses are mounted on 3D translation stages to adjust

30

Figure 3.3: Typical spectrum and FROG trace of the amplifier output.

31
the focus positions. The vacuum chamber window is a 3 mm thick sapphire window inexperiments presented in Chapters 3, 4 and 6.

3.1.2

Generation chamber and gas injection

The HHG chamber shown in Fig. 3.4 is equipped with a high speed 550 l/s Turbopump. The diameter of the connection between the chamber and the pump is 6 inches
to ensure maximum pumping efficiency. The atomic or molecular beam is injected into
the chamber with a continuous jet made of a ∼1 cm long hollow glass fiber that has
a 125 µm inner diameter and a 1.25mm outer diameter respectively. The capillary
was glued to a glass tube which extends to the outside of the vacuum chamber by afeedthrough, and is connected to the gas cylinder through an UltraTorr connection. Ourbacking pressure is usually around 1 atmosphere and controlled by the regulator of thegas cylinder.
Supersonic cooling of the molecular beam has many applications in physics andchemistry, such as high resolution molecular optical spectroscopy and molecular reaction dynamics. The high pressure gas goes through a pinhole into a vacuum chamber.
Collisions during the adiabatic expansion strongly reduce the translational energy of
the atoms or molecules. Rotational cooling was achieved by the equilibration between
the translational and rotational degrees of freedom, thus transferring the population tolower energy rotational states. As the expansion continues, collisions cease, and thelowest temperature is achieved.
With the help of a pulsed jet, high backing pressure, a carrier gas, and skimmers,
rotational temperature less than 10K can be achieved by supersonic cooling. However,for the HHG experiments, a reasonably high gas density was needed in the interaction
region to generate sufficient HHG flux. Therefore we use a continuous jet to run theexperiments at the full repetition rate available from the laser, since kHz pulse valves arestill not widely available. This limits the lowest rotational temperature we can achieve,

32

Barrel Shock

M<1

Mach Disk ShockM<1

Background Pressure

M<1

-2

pressure with gas input 10 Torrpressure with gas

Zone of Silence
M >> 1-4

input 10 Torr

Jet Boundary
200nm Aluminum Filter

Nozzleas differential pump stage

1cm

To gas line: stagnation pressure700-1000 torr
Stagnation Pressure
P0 , T0, M << 1

Figure 3.4: The design of the harmonic generation chamber with an illustration of thegas injection.

33
because we also need to keep the background pressure in the chamber low enough to
avoid reabsorption of the generated EUV light.
To estimate the gas flow rate, the gas density distribution, and the rotationaltemperature in the interaction region, we need to know the chamber volume and thepump speed, as well as the jet parameters discussed above. We estimate that the onaxis gas density 500 µm downstream from our jet is approximately 1018 cm−3 , and therotational temperature is approximately 100 K for CO2 molecules. The total pass lengthof the gas medium is less than 1mm.
However, the error bar of this estimate is usually quite large. This is due to threefactors. First, the length of the final fiber section of the jet was not accurately controlled
in fabrication. Second, the distance between the laser focus and the gas jet exit was notaccurately controlled in the experiments. Third, the fiber section was made of glass,and thus can be slightly damaged by the focused laser beam due to misalignment.
Due to the short pass interaction length of the jet, we ensure that the short
trajectory HHG is fully phase matched —the coherence length is much longer thanthe medium length—by focusing the laser beam slightly before the gas jet, where theharmonic flux is also maximized. This is very important to our experiments, because
the macroscopic HHG is proportional to the HHG from a single atom or molecule only
under the phase-matching condition.
In addition to phase matching issues, other macroscopic effects, such as plasma
defocusing and self phase modulation of the fundamental pulse can afftect the HHG.
Again, due to the short interaction length in our gas jet, we usually neglect these effects.

3.1.3

Imaging of the focus

For our experiments, the spatial profile is important for estimating the laser
intensity at the focus. We built an imaging system to measure the beam profile in-situ.
We placed a removable steering mirror 15 cm from the gas jet along the optical beam

34
propagation direction to reflect the beam out of the vacuum chamber.. The beam thengoes through a 40-cm focal length imaging lens and two intensity attenuators, and is
finally detected by a web cam at the image plane. We image the beam profile at thegas jet position. Although the beam focus is slightly before the gas jet, we can a very
good estimation of the focused beam size and profile.

3.1.4

Detection of the HHG light

The generated harmonics pass through two 200 nm thick aluminum filters to reject
the fundamental laser light. The transmission curve of this filter is shown in Fig. 3.5 (c).
The HHG beam is then spectrally dispersed using an EUV spectrometer (containing a
grazing incidence cylindrical gold mirror and EUV grating, made by Hettrick Scientific)
and finally detected using an EUV charge-coupled device (CCD) camera. We useda back-illuminated CCD camera from Andor Technology with a spatial resolution of
1024×256. A typical experimental harmonic image recorded by the CCD is shown in
Fig. 3.5 (a). The image on the CCD has line structures due to the 1D focus of thecylindrical gold mirror. In the fully vertical bin mode of the camera, the photon counts
can be electronically integrated along the short camera dimension (256 pixels). A typical
HHG spectrum from CO2 , along with the transmission curve of the aluminum filter, areshown in Figs. 3.5 (b) and (c). In practice, the transmission of the aluminum filter will
decrease with time due to oxidation on its surface.

3.1.5

Data acquisition and analysis

Processing of raw spectral data from the CCD starts with subtracting a background from the raw spectrum. The background includes two parts, the dark noise of
the CCD camera (which is dominant), and the scattered HHG and remaining fundamental photons. Following background subtraction, the harmonic intensity was integrated
among the pixels that see significant flux. The wavelength scale are calibrated by the the

35

(a)

(b) 800019
21

Amplitude (Arb. Unit)

7000
6000

17
23

5000
4000
25

3000
27

2000

29

15

31
35

1000
0

(c)

31
2nd order29
2nd order

200

400
600
CCD pixels

800

39

1000

Figure 3.5: (a) and (b) Typical 2D image and fully vertical binned spectrum of the
HHG from CO2 taken by the CCD camera. (c) Transmission of a 200 nm aluminum
filter.

36
aluminum absorption edge at 72.4 eV and further confirmed by identifying the positionof the second order diffraction of the grating.

3.2

Nonadiabatic molecular alignment
In our experiments, a ∼100 fs pump pulse is used to align the molecules, thisduration is much shorter than the rotational period of the molecules used (usuallytens of ps). This allows us to align the molecular sample in the non-adiabatic alignment
regime. Note that the intensity of our pump pulse is below 6×1013 W/cm2 , so ionizationof the sample can safely be ignored.

3.2.1

The interaction Hamiltonian

The alignment of the molecules can be understood through the torques createdby the electric field interacting with the induced dipole τ = p × E, where p = α · E
is the induced dipole. However, a classical model cannot fully characterize rotational
revivals, due to the quantized nature of rotation levels. Each rotational eigenstate,|JM i, has an energy BJ(J + 1), where B is the rotational constant of the molecule, andis inversely related to the moment of inertia: B =h̄2. The field-dressed pendular states
2I

are govern by the time-dependent Schrödinger equation (TDSE). We start by deriving
the Hamiltonian H = H0 + HL for a linear molecule in an optical field. The moleculeinteracts with light through the dipole operator.
1
HL = −µ · E − p · E,
2

(3.1)

where µ is the permanent dipole of the molecule. The electric field is a cosine oscillation
E(t) = êa(t)cos(ωt + ψ), where a(t) is the pulse envelope. We note that the interaction
related to the permanent dipole will be averaged out and will not contribute to thepotential energy.

37
In the molecular frame, the polarizability tensor α can be written as


 α⊥


α=
 0



0

0
α⊥
0



0 



0 




(3.2)

αk

where αk and α⊥ are the polarizability along and perpendicular to the molecular axis,∆α = αk − α⊥ is the difference between them, and the angle θ is the angle between thelaser polarization and the molecular axis. Thus the interaction term can be written as:




1
1
− E 2 (t) αk cos2 θ + α⊥ sin2 θ = − E 2 (t) ∆α cos2 θ + α⊥ .
2
2

(3.3)

Since the second term is not angle-dependent, we neglect it for convenience. Averaging
over the laser oscillation, the first term can be written as:1− a2 (t)∆α cos2 θ
4

(3.4)

The field-free Hamiltonian is BJ2 , so the total Hamiltonian can be written as:
1
H = BJ2 − a2 (t)∆α cos2 θ
4

(3.5)

The rotational constant B and the anisotropic polarizability ∆α for simple molecules
can be found at [31]. We list a few example molecules in Table 3.2.
Table 3.2: The rotational constant, rotational period, and anisotropic polarizability forseveral common molecules
Molecule
H2
N2
O2
CO2
N2 O

Rotational Constant, B
60.853 cm−1
1.99 cm−1
1.43 cm−1
0.39 cm−1
0.43 cm−1

Rotation period (ps)
0.274
8.383
11.66642.69939.805anisotropic polarizability, ∆α0.288 Å3
0.7 Å3
1.1 Å3
2.1 Å3
2.8 Å3

38
3.2.2

Solving the TDSE

The rotational wave functions |JM i are mathematically equal to spherical harmonic functions. The matrix element hJM |H| J ′ M ′ i between two rotational states|JM i and |J ′ M ′ i, is mostly zero, except for J = J ′ or J = J ′ ± 2 and M = M ′ . Thus
the matrix form of the time-dependent Schrödinger equation can be simplified to a seriesof differential equations. Each equation corresponds to a specific |JM i state.
As we mentioned in the experimental section, we estimate the rotational temperature at the interaction region is about 100K. At this temperature, only the rotational
states of the molecules with Ji < 40 can be thermally excited. The population is
distributed among the rotational states according to the Boltzmann distribution. Neglecting the rotational states for Ji > 40, the initial state of the molecular ensemble canbe described by a density matrix:
Ji,maxJi
X
1 X|Ji Mi i hJi Mi |wJi e−iEJi /kT
Qrot J =0
M =−J
i

i

i

where the rotational partition function can be written as:
Ji,maxQrot =X

wJi (2Ji + 1)e−iEJi /kT ,

(3.6)

Ji =0

where the factor wJi are related to the nuclear spin statistics.
We can propagate this initial state density matrix under the Liouville equation.
Equivalently we can also assume the initial state is a pure |Ji Mi i state. We thencalculate the time evolution of this pure state by solving the TDSE . Finally when the
expectation value of an observable operator is calculated, an incoherent thermal averageis needed. Thus, the final state after excitation for the initial state |Ji Mi i can be expressed as a coherent rotational wave packet in terms of the rotational eigenstates |JM iwith complex coefficients, CJM,Ji Mi (t), and energy-dependent phase accumulation:

ψJi Mi (t) =X

J,MCJM,Ji Mi (t)e−iEJ t/h̄ |JM i =XJ,MCJM,Ji Mi (t)e−iBJ(J+1)t/h̄ |JM i (3.7)

39
3.2.3

The expectation value and thermal averaging over initial states

We can calculate the expectation value of operator Ô by hψJi Mi (t)| Ô |ψJi Mi (t)i.
The typical operators used to characterize the molecular alignment are the angulardensity hψ(t)|ψ(t)i and the expectation values of cos2 θ and sin2 2θ. These values arecalculated for each initial state, and then added incoherently, weighted by the thermal
populations:Ji,maxJi
X
1 X
wJi e−iEJi /kThψJi Mi (t)| O |ψJi Mi (t)iQrot J =0
M =−J
i

i

(3.8)

i

The rotational wave function |JM i can be represented by the spherical harmonics
Ylm (θ, φ), and the integration of this is trivial. A C++ code solving this TDSE and calculate different expectation values was developed by Dr. Andreas Wüest and Robynne
Lock [32].
We are particularly interested in the angular density ρ(θ, φ, t), here:
Z π
0

dθ

Z 2π

dϕρ(θ, ϕ, t) sin θ = 1

0

Due to the rotational symmetry around the aligning laser, ρ(θ, φ, t) is independent of theazimuth angle Φ. We can define a new function ρ(θ, t) to represent the time-dependent
angular distribution:ρ(θ, t) = 2πρ(θ, ϕ, t) sin θ,
here

Z π

dθρ(θ, t) = 1.

0

We note from our experiments that a good balance of the pump pulse intensityand duration can improve the alignment. We found the optimum pulse duration andintensity for alignment is approximately 100 fs and a few times 1013 W/cm2 .

3.2.4

Periodical revivals after time zeroFigs. 3.6 and 3.7 present the molecular alignment for CO2 and N2 molecules, characterized by the angular distribution hψ(t)|ψ(t)i and the expectation values of cos2 θ

(a)
n

(c)

(b)

Figure 3.6: This figure shows (a) hcos2 θi and (b) hsin2 2θi of CO2 during a rotational period and (c) the angular distribution ρ(θ, t) for
isotropic molecules and strongly aligned and antialigned molecules during half revival.
40

41

(a)

n

2

(b)

Figure 3.7: This figure shows (a) hcos2 θi and (b) hsin2 2θiof N2 during a full rotational
period .

42and sin2 2θ. We confirm, by numerical simulation, that experimental angular distributions are not critically dependent on parameters such as rotational temperature or laser
intensity.
At certain time delays after the pump pulse, the excited wave packet will rephaseto form a revival. The reason for this periodic behavior is that the wave packet is composed of rotational eigenstates with discrete energies BJ(J + 1)h̄. Under field free conditions, the Hamiltonian is independent of time, therefore, the coefficients CJM,Ji Mi (t)are independent of time. The evolution of the wave packet comes from the different
phase accumulation of rotation levels of different eigenenergies. Consider a time delayT =πh̄, the phase of each state changes by πJ(J + 1), which is a multiple of 2π forB

all positive values of J. This means the wave packet at this time (and multiples of thistime) repeats the wave packet at t = 0. The time T =πh̄, is called the full revival time.
B

There are fractional revivals at fractions of the revival time T (i.e. 1/2, 1/4, 1/8, . . .),during which only a portion of the states are in phase. Some of these revivals are notshown in alignment parameters hcos2 θi or hsin2 2θi, they can only be seen from the timedependent angular distribution ρ(θ, t).

3.3

HHG from aligned molecules

3.3.1

Coherent buildup of HHG

Replacing the ground state of an atom with the HOMO of certain molecules, we
can generalize the Lewenstein model for the case of HHG from molecules.
D(t) = hψ(t)| r |ψ(t)i =
=i

Z t
0

dτ

Z

Z

d3 vd∗x (v)b(v, t) + c.c.

d3 p cos(ωτ )d∗ (p − A(t))e−iS(p,t,τ ) [E · d(p − A(τ ))] + c.c. (3.9)

This model has been used to calculate the angular dependence of HHG [33, 34, 35]. In
the Lewenstein model, the ionization is characterized as the transition dipole d(p−A(τ ))43
between the ground state and the continuum state, which is different from the ionization
rate calculated with the molecular ADK theory.
We can calculate the HHG amplitude S(Ω, θ) through the Fourier transform of
the time-dependent dipole. Assuming the molecular angle does not change on the timescale of the ultrashort pump pulse, the total harmonic intensity can be written as an
convolution of the single-molecule HHG amplitude with the angular distribution:
SA (Ω, t) =Z 2πρ(θ, t)S(Ω, θ)dθ

(3.10)

0This equation is rigorously proved in ref. [36], using the density matrix formula.

3.3.2

Tomography of the molecular orbital

In the integral of the Lewenstein model (Eqn. 3.9), the information about themolecular structure is contained in the dipole term d∗ (p − A(t))d(p − A(τ )). A very
general method for probing molecular structure using HHG was demonstrated recently
by using a tomographic technique to reconstruct the N2 molecular orbital [37]. Basically, the return electron wave packet in the HHG process is considered to be a planewave, and from this it is assumed that the HHG intensity can be characterized by
the angle-dependent ionization N (θ), the return electron wave packet a(k(Ω)) and therecombination dipole between the plane wave and the HOMO.
Under the single active electron approximation the recombination process is acontinuum to bound (HOMO) transition. For harmonics with frequency Ω = nh̄ω, thereturn electron wave packet can be written as |ψc (t)i =Pa(k(Ω))eik(Ω)x−iΩt , whereΩa(k(Ω)) is the complex amplitude of the return electron wave packet and the transition
dipole between the continuum wave function ψc (t)and the ground state HOMO ψg canbe written as:dL (t, θ)= hψg (r, θ)| r |ψc (t)i

44
=

X
Ω

=
=

Z

Z

E

a(k(Ω)) hψg (r, θ)| r eik(Ω)x e−iΩtEa(k(Ω)) hψg (r, θ)| r eik(Ω)x e−iΩt dΩa(k(Ω))dL (Ω, θ)e−iΩt dΩ,(3.11)

where θ is the angle between the driving laser polarization and the molecular axis. From
this, we can derive the following definition which relates the dipole moment to the 3D
E

Fourier transform of the molecular orbital: hψg (r, θ)| r eik(Ω)x = dL (Ω, θ). In length
gauge this can be expressed as:S(Ω, θ)hi2= |H(Ω)|2 = F d̈L (t, θ)= Ω4 |F [dL (t, θ)]|2 |a(k(Ω))|2= Ω4 |a(k(Ω))|2 |dL (ω, θ)|2 ;(3.12)and in velocity gauge this can be expressed as:Ehψg (r, θ)| v eik(Ω)x = dV (t, θ),andS(Ω) = Ω2 |a(k(Ω))|2 |dV (Ω, θ)|2 ;in acceleration gauge this can be expressed as:Ehψg (r, θ)| a eik(Ω)x = dA (t, θ),andS(Ω) = |a(k(Ω))|2 |dA (Ω, θ)|2 .
According to the three-step model, the harmonic power spectrum generated fromaligned molecules not only depends on the recombination dipole, but also on the angledependent ionization. With this considered, we can rewrite the harmonic power spectrum as [37]:HHG(Ω, θ) = |S(Ω, θ)|2 = N (θ)Ω4 |a(k(Ω))|2 |dL (Ω, θ)|2

(3.13)

45
where N (θ) is proportional to the angle-dependent ionization rate. A few assumptions
and arguments need to be made to extract the wave function:(1) It is assumed that for each pump/probe angle θ, the intensity HHGN2 (Ω, θ)from a perfectly aligned molecule is measured. The convolution with the angular
distribution is neglected. The perpendicularly polarized HHG component when
the pump and probe pulse polarization are not perpendicular or parallel to eachother is also neglected.
(2) Since Ar atoms and N2 molecules have similar Ip [37], it is assumed that therecolliding electron wave packets are the same for Ar and N2 , thus the HHG
spectrum from Ar can serve as a reference.
(3) A phase jump occurs at the 23rd harmonic, based on the fact that there is aspectral minimum in the normalized HHG spectrum of N2 .
(4) For nitrogen molecules, the angularly dependent ionization and the spatial
spreading of the electron wave packet can compensate for each other; thus bothcan be ignored.
Based on these arguments and assumptions, the following relation can be obtained:
SN2 (Ω, θ)
dN2 (Ω, θ) =dAr =SAr (Ω)p

HHGN2 (Ω, θ)eiφr
pdAr ,HHGAr (Ω)

where φr is the relative phase between the emission dipole of N2 and Ar.

Since

E

dN2 (Ω, θ) = hψg (r, θ)| r eik(Ω)x , the Fourier slice theorem can be used to tomographically reconstruct the HOMO of the molecules from the HHG measurement at 19 different
angles θ, similarly to how images are reconstructed in medical tomography.
The significance of this experiment lies in the fact that, since the return electron
has a wavelength comparable to the molecular dimension, and since HHG can be considered as the interference of the plane wave continuum electron with the ground state,molecular information is encoded in the HHG properties.

46

3.4

Recent theoretical advances
As we have shown, the three-step model is central to our understanding of HHG

from molecules. However, a few important approximations have been made in thismodel, compared with the case of a full quantum calculation.
First, the single active electron approximation does not include the multi-electron
effects such as the indistinguishability of electrons and spin statistics [38, 39].
Second, the correlation between the continuum and bound electron during boththe ionization and electron propagation are not considered. For a rigid molecule, such as
N2 , the Koopmans’ approximation is valid, which means the cation has the exact sameN-1 electron wave function as the neutral. This also means that the Ip of the molecules
is the energy level of the HOMO electron. However this is not true for molecules withlarge polarizability.
Third, since the ionization rate is exponentially related to the ionization potential,
for atoms the outer-most electrons are much easier to ionize than the lower lying states,
In this case, it is safe to consider only the highest orbital during the strong field process.
Thus single ionization channel is assumed, which means the electron being ionized isalways from the HOMO. This is equivalent to the statement that only the ground stateof the cation is accessed as shown in Fig. 3.8. This approximation does not apply formolecules with closely lying cation states.
Finally and more importantly, in the sense of the strong field approximation(SFA), the influence of the Coulomb potential on the recolliding electron is not considered [40]— an electronic plane wave was used to represent the recolliding electron.
Furthermore, at the recollision, the molecules were assumed to be at field free condition.
The various approximations listed above have motivated intense theoretical efforts
to extend the 3-step model beyond the SFA and SAEA [13, 14, 16]. However, thevalidity of these new and more sophisticated theories needs to be compared carefully

47

(a)

(b)

Cation excited state

Cation ground state

Neutral Ground state

Neutral Ground state

Figure 3.8: The schematics for tunnel ionization from HOMO to cation ground state(a) and from HOMO-1 to cation excited state (b).

48
with experiments.

3.4.1

Multielectron and multichannel ionization

To account for multielectron effects, instead of considering the dipole moment ofa single electron, we can consider the dipole of a multielectron wave function:
NX

D(t) = ehψ(r1 , ..., rN )ri ψ(r1 , ..., rN )i(3.14)

i=1

If we neglect the correlation between the continuum and bound state during the electron
propagation, we can write the dipole as:ψ(r1 , ..., rN ) = ψg + ψc = ψg (r1 , ..., rN ) +XjÂψion,j (r1 , ..., rN −1 )ψc,j (rN )(3.15)

Where ψg is the N-electron ground state of the molecules and ψc is the N-electronstate with one electron in the continuum. The anti-symmetric operator Â is used toaccount for the indistinguishability of electrons and spin statistics. The index j labels
the different ionization channels, which means that more than one cation states canbe accessed by the tunnel ionization. Plugging Eqn. 3.15 into the dipole equation, we
obtain,D(t) =

Xjehψneutral (r1 , ..., rN )

N
X
i=1

ri Aψion,j (r1 , ..., rN −1 )ψc,j (rN )i.

The continuum wave function can be solved by scattering method [40]. The boundwave function is represented by the Dyson orbital of different ionization channels. The
Dyson orbital hψneutral (r1 , ..., rN )|ψion,j (r1 , ..., rN −1 )i is the inner product of the Nelectron neutral wave function and the (N-1)-electron cation wave function. Thus, thedipole can be considered as the recombination from the continuum wave function to the
Dyson orbital.

49
3.4.2

Recombination as an inverse process of photoionization

In a recent paper [41], based on an extension of the three-step model, it was shownthat accurate HHG intensity can be expressed as
HHG(Ω) = W (Ek ) |dR (Ω)|2Here W (Ek ) describes the flux of the returning electron with energy Ek , and can becalculated by dividing the SFA calculated dipole SSF A (Ω) by the plane wave recombination dipole. This was confirmed by TDSE calculations of atoms and the molecular ion
H+
2 [42]. dR (Ω) is the exact photoionization transition dipole of the molecules ionized
by a photon with energy h̄Ω. It can be derived from the differential photoionization
cross section along the laser/EUV polarization [43]. Since the continuum wave function
is different for the photoionization process compared with the HHG process, more work
is needed to fully verify this theory.

Chapter 4

Phase and Intensity Characterization of HHG Emission from Aligned
Molecules

As we discussed in the previous chapter, the continuum-bound transition in the
HHG recombination process converts the kinetic energy of the electron into an EUV photon. Information about the molecular structure is encoded in the orientation-dependenceof the HHG intensity.
As a simple example, the shape and symmetry of the HOMO can result in multicenter quantum interferences as the electron recombines. This is in exact analogy to
the same effects long-recognized in the context of EUV photoelectron spectroscopy ofmolecules [44], since recombination in HHG is similar to the photoionization process.

4.1

Two-center interference in molecular HHG
Lein et al. theoretically investigated quantum interferences in HHG from hydro-

gen molecules by solving the time dependent Schrödinger equation (TDSE) [45, 46]. A
spectral minimum was found both in the harmonic spectrum for a fixed orientation, andin the angular dependence of the harmonic intensity for given harmonic order. Furthermore, this work predicted a sudden phase jump at the spectral minimum, where thephase of the electric field of the high harmonic emission reverses. These results can beunderstood as interference of harmonic emission from two spatially separated atomic
orbitals in a molecule as illustrated in Fig. 4.1. The evolution of HHG intensity during

51
a full rotational period of CO2 for harmonic order 23, 33, and 37 are shown in Fig. 4.2.
We also plot the alignment parameter cos2 θ on the top of Fig. 4.2, this parameter iscalculated at 105 K rotational temperature and 5.5×101 3W/cm2 pump pulse intensity.
D

The recombination dipole can be written as S(Ω, θ) = eik(Ω)·r Ô |ψi, where Ô
is the velocity gauge dipole operator and |ψi is the molecular HOMO. If |ψi can be
1RR
written asφ(r − ) ± φ(r + ) , then S(Ω, θ) can be written as,
2
2
2




S(Ω, θ) =DRR1) ± eik·r Ô φ(r + ) √
2
2
2

Z
Z
R
1
R
=
e−ik·r Ôφ(r − )dr ± e−ik·r Ôφ(r + )dr √
2
2
2

Z
Z
R
1
)
−ik·(r−)−ik·(r+ R
2 Ôφ(r)dr ±2 Ôφ(r)dr √
e
=
e
2


Z
R
R
1
= (e−ik· 2 ± e+ik· 2 ) e−ik·r Oφ(r)dr √ .
(4.1)
2
D



D

eik(Ω)·r Ô |ψi = eik·r Ô φ(r −For ‘+’ sign atomic orbital superposition,S(Ω, θ) =√R) e−ik·r Oφ(r)dr2√R= 2 cos(k · )d(Ω, θ).
2=

2 cos(k ·

Z

(4.2)

For ‘-’ sign atomic orbital superposition,S(Ω, θ) =Z√R= − 2i sin(k · ) e−ik·r Oφ(r)dr2√
R= − 2i sin(k · )d(Ω, θ).
2

(4.3)

The two-center interference model was discovered through the simulation of H2 ,which is a ‘+’ superposition of two atomic s orbital. However it is relatively difficult toalign (because of its small anisotropic polarizability, ∆α = 0.288Å3 ). Furthermore therotational period is short (274 fs for H2 ) makes very short (10 fs) pulse a necessity.
CO2 is an excellent candidate for studying harmonic phase effects because it ishighly polarizable (∆α = 2.109Å3 ) and easy to align, The degenerate HOMO of CO2
has a ‘two-center” character similar to H2 , but it is a ‘-’ sign superposition of carbon py
or px orbital rather than ‘+’ sign superposition of H2 .

52

Electron wave

λOӨcoherent sum

OC

R cos ӨR

CO2 molecules

Figure 4.1: Illustration of the recolliding electron plane wave and the quantum interference of HHG in CO2 molecules. Figure credit: Gregory J. Kuebler.

53

<cos

2

>

T=105K

Pump Intesity=5.5x10

13
2
W/cm

0.8
0.6
0.4
0.2
0

10

20

30

40

30

40

Harmonic 21st

2
1
0
0

10

20

4

Harmonic 31st

2

0
0

5

10

15

4

20

25

30

35

40

45

30

35

40

45

Harmonic 35th

3
2
1
0
0

5

10

15

20

25

Pump/Probe time delay (ps)Figure 4.2: The evolution of HHG during a full rotational period of CO2 for harmonicorder 23, 33, and 37 with the alignment parameter cos2 θ .

54
In past work, Kanai et al. and Vozzi et al. attributed the observed alignment
dependence of the harmonic emission from CO2 molecules to quantum interference [47,48]. However, the harmonic orders most strongly modulated by alignment differedin the two experiments (the 25th vs the 31st orders, respectively). Furthermore, theauthors found that different relationships between the harmonic photon energy andthe recolliding electron kinetic energy, Ek = nh̄ω or Ek = nh̄ω - Ip , best fit theirexperimental data, where nh̄ω is the harmonic energy and Ip is the molecular ionization
potential. These two different relationships correspond to slightly different physicalpictures—the latter corresponds to the case where the recolliding electron interacts
with the HOMO and generates emission when it returns to the edge of the molecularpotential, while the former implies that HHG occurs when the electron returns to the”bottom” of the molecular potential, and is thus accelerated by the Coulomb field of
the molecule ion.
Other than interference, ground state depletion was also proposed as a possible
mechanism for the observed modulations [49]. Therefore more accurate measurementsof both the phase and intensity of HHG from aligned molecules are important, bothto confirm conclusively that quantum interferences do exist in molecular HHG, and toprovide insight on distortion of the recolliding wave function by the Coulomb potentialof the ionized molecule. Measurement of the phase of the high harmonic emission is also
critical for new approaches to molecular imaging [37]. While past experiments [50, 51]
provided some evidence for phase jumps in HHG, they were inconclusive in making
accurate comparisons with the two-center model.
√kR cos θ
In Fig. 4.3, we plot the prefacter 2 sin(
) for CO2 molecules. The2h̄
wavelength of the returning electron wave is obtained from the relation λ = √2mEk
where m is the electron mass and Ek is the kinetic energy of the electron. The condition
for the interference minimum is R cos θc = λ, which is a condition that is satisfied
within the harmonic spectral range that is experimentally accessible. For a harmonic of55

Figure 4.3:
molecules.

The prefacter√2 sin(

kR cos θ) from two-center interference for CO22

56
wavelength λ, the sign of the recombination matrix element S(Ω, θ) reverses for angles
below and above θc . A few subtle points about the two-center interference model mustalso be considered. We list them in the following:1RR(1) The fact that the molecular HOMO can be written asφ(r − ) ± φ(r + )
2
2
2




does not mean the molecules are bonding (antibonding), or symmetric (antisymmetric) in terms of the mirror symmetry. The accurate description of twocenter structure is that after a translation of distance R , the two atomic orbital
can exactly overlap with each other [52].
(2) The term d(Ω, θ) =R

e−ikr Oφ(r)dr is still a function of angle θ. For hydrogenmolecules, this is not obvious, because the HOMO is a symmetric superpositionof two isotropic s orbitals. But for CO2 , which is a superposition of two φ(r) is
p orbitals, the dipole d(Ω, θ) depends on the angle θ between k and r. However,in most cases the prefactor of two-center interference will dominate the angulardependence of HHG.
(3) The phase of HHG Φ(n, θ) is a function of the harmonic order n and molecularorientation angle θ. It consists of two parts according to the Lewenstein model:
the intrinsic phase that is accumulated in the continuum and the phase of recombination dipole. The intrinsic phase, which gives a chirp of the generated
attosecond pulse, depends on the ionization potential Ip and harmonic order,
but does not depend on molecular orientation, while the phase of recombination
dipole depends on the molecular orientation.
(4) If we plot the prefactor√

2 sin(

kR cos θ) for CO2 , we can clearly see that the2value of this factor has a different sign between [0,π/2] and [π/2,π]. This must
be an artificial effect because the nuclei of the molecules are fully symmetricaround the laser polarization [53]. The reason of this effect is that we break up

57
the correlation between the continuum and bound electron. Since the electron
wave packet is ionized from the most probable region in the molecules (the lobe
along the laser polarization), it actually changes sign when molecules rotate fromθ to π − θ angle. The HOMO does not have an absolute phase, therefore therelative phase between the return electron plane wave and the HOMO determine
the phase of the recombination dipole. This argument can be confirmed by a
TDSE calculation of a simple molecule with ’-’ sign superposition of atomic
orbitals.
(5) In the derivation of the two-center interference model, we use velocity gauge
operator instead of length gauge. Since the wave function we use to calculate
the dipole is not an exact wave function, the result depends on the gauge used.
Previous studies have shown that the velocity gauge gives a better agreementwith the TDSE calculation than the length gauge [54].
In this section we first use a gas-mixture method to extract the alignment dependent phase of HHG from molecules, where the HHG emission from an atomic gas
is used as a reference [51]. Second, we present the first direct and accurate measurement of the phase of harmonic emission from molecules [55]. We directly confirm thata two-center interference in the CO2 and N2 O HHG emission induces a minimum atcertain angular distributions, with a corresponding phase shift of π. We fit the harmonic
emission as a function of time within a rotational revival to the two-center interference
model convolved with the rotational distribution, which allows us to extract the ratioof the two-center separation in the molecule to the returning electron wavelength as afunction of harmonic order. The data show that the contribution from the molecularpotential on the electron kinetic energy varies with harmonic order, and as a result, therelationship between the harmonic energy and the recolliding electron kinetic energy
also changes. These results have important implications for efforts to extract molecular

58
structure from measurements of the harmonic emission from molecules, and can be used
to benchmark realistic theories of molecules in strong fields.

4.2

Using gas mixtures to measure the phase of molecular HHG
Recently we have used a mixture of atomic and molecular gas to indirectly mea-

sure the phase of the HHG emission from molecules[51, 56]. Consider a mixture of an
atomic (Kr) and a molecular (CO2 ) gas. The emission intensity of a single harmonicorder generated from a mixture of an atomic (Kr) and a molecular (CO2 ) gas. is thenthe coherent sum of the emissions from both species.
The total emission from CO2 is a coherent convolution of HHG from perfectlyaligned molecules and the angular distribution function ρ(θ, t).
After exciting the rotational wave packet in CO2 , the magnitude (SCO2 ) and phase(φCO2 ) of the harmonic emission depends on the wave packet evolution and will varywith the time delay between the pump alignment pulse and probe harmonic-generation
pulse.

SA,CO2 (Ω, t) =Z πS(Ω, θ)ρ(θ, t)dθ

(4.4)

0

We can split the HHG amplitude from CO2 and Kr as magnitude and phase terms,
SA,CO2 (Ω, t) = ACO2 (Ω, t) exp(iφCO2 ) and SKr (Ω, t) = AKr (Ω, t) exp(iφKr ) The total
harmonic intensity from the mixture gas with fraction a(0 < a < 1) of CO2 can be
written as
HHG(a)= |aACO2 exp(iφr ) + (1 − a)AKr |2= a2 A2CO2 + (1 − a)2 A2Kr + 2ACO2 AKr a(1 − a) cos φCO2

(4.5)

while φr (θ) is the phase of the emission from CO2 relative to krypton.
The atomic phase from unaligned CO2 and Kr are the same, since they have
similar Ip . Therefore, φr (θ) is the relative phase mostly comes from the recombination

59
step. We take the temporal scan for rotational period of the CO2 and Kr mixture. With
the HHG intensity of pure CO2 and Kr measured, We can first solves the complex HHG
dipole for CO2 .
The rotational wave packet angular probability density is well understood andcan be calculated [57] as we discussed in the last chapter. It is therefore possible toretrieve the orientational dipole from the measured time-dependent harmonic emission
from rotationally excited molecules and atomic gas mixtures.
Although we observe phase change when the molecules are aligned from the gas
mixture data, this method is inaccurate because the fraction a is not a well-controlledparameter. Even given a pre-measured mixture of gases, due to the different adiabatic
constant γ of CO2 and Kr, the real fraction in the interaction region will be different
from the original mixture ratio. The rotation temperature and density distributions also
depend on a. The recombination phase of Kr is not well-known, because the structureof atoms can result in phase variations as well [58].

4.3

Double-focus interferometry for simultaneous intensity andphase measurement
Hakan TureciTo determine the variations in the phase of HHG emission, an in-

terferometry measurement is ideal. Although a double-focus interferometric geometry
has been used before to measure the coherence of HHG and the atomic dipole phaseof HHG [59, 60], here we use a new geometry that is both exceedingly stable and simple to implement. Beam path-length stability is especially critical for interferometricmeasurements due to the short wavelength of the harmonic light. We use two glass
plates tilted at slight angles, and partially inserted into the focusing laser beam (2∼3
cm after a lens of 30 cm focal length), to split the focus into two elliptical focal spots
with diameters (full width at half maximum) of ∼80 µm, as shown in Fig. 4.4. The
transverse distances between the two foci and the exit of a continuous gas jet with 150

Harmonic generation pulse

non-collinearalignment pulse

HHG interference
on CCD camera
HHG from aligned
molecules
HHG from isotropic
molecules

window

gas jet

27
25

29
27

29
31

Figure 4.4: Schematic setup for directly measuring the intensity and phase of high harmonic emission from molecules. HHG from aligned
and randomly oriented molecules from two different regions interfere in the far field. Figure adapted from [55].
60

61µm diameter are 110 µm and 240 µm respectively. The stagnation pressure of the gas
is 700 Torr. The duration of the harmonic generating pulse is 25 fs, with 550 µJ ofenergy in each focal spot, corresponding to a focal intensity of about 2.5×1013 W/cm2 .
To select harmonics originating from the short trajectories, the focal positions of bothfoci are slightly before the gas jet. The harmonics from these two regions emerge andinterfere in the far field. Slight adjustment of the angles of the two plates can change
the distance between the two foci, and the relative angle between them can change thetime delay. A second beam with the same polarization and containing 320 µJ of energy
in 120 fs is focused non-collinearly (crossing angle < 2 degrees) into the molecular gas
at the position of one focus, at an estimated intensity of 4–6×1013 W/cm2 , to create atransient molecular alignment. The HHG from the unaligned focus serves as a constantphase reference. Any fringe shift observed will arise from a phase change of HHG fromthe aligned molecules. By blocking the high harmonic generation laser pulse in the unaligned region, we can characterize the harmonic emission from the aligned molecules.
A flat-field cylindrical focus grating spectrometer dispersed the harmonic spectrum andimaged the harmonic in one dimension onto an EUV CCD. Stable EUV interference
fringes were observed for harmonic orders up to order 31, since the divergence of the
HHG emission from the two regions causes a spatial overlap on the CCD in the nonimaging direction. Above order 31, the divergence and intensity of the beams is too
small in our geometry to observe fringes. A similar setup was also reported recently.

4.4

Quantum interference in CO2 molecules
Fig. 4.5 (a) shows the net harmonic intensity for orders 19–45 as a functionof time delay between the alignment and harmonic generation pulses through the 3/4
revival, where the molecules can be most strongly aligned. These data exhibit a very
different behavior for harmonics above and below the 27th. To see this more clearly,

62
47
Harmonic order

43

(a)
6

39
35

4

31
2

27
23
(b)

2

<cos θ>

1
0.8
0.6
0.4
0.2
−1000

−500

0
Time delay (fs)

500

1000

(c)

Figure 4.5: (a) Experimentally measured intensity (from the aligned molecular sample
only) for harmonic orders 19 - 45 as a function of time-delay between the aligning laser
pulse and harmonic-generating pulse within the 3/4 revival. Time zero is shifted tothe center of this revival for convenience. (b) Predicted cos2 θ alignment assuming
a rotational temperature of 105 K. The inset plots the angular distribution at threeselected times within the revival, color coded to indicate the corresponding time on thecos2 θ graph. Here, 0◦ corresponds to alignment along the laser polarization, while90◦ corresponds to ”anti-alignment.” (i.e. perpendicular to the laser polarization) The
critical angle of 34◦ for harmonic order 31 is also labeled. Figure adapted from [55].

63
lineouts of different harmonics are shown in Figs. 4.6. Below order 27, the intensity
follows an inverse of the cos2 θ ensemble averaged alignment parameter (shown in
Fig. 4.5(b)); i.e. HHG emission is minimum when the molecule is aligned parallel tothe laser polarization. In contrast, for harmonics > 27, the yield first goes througha minimum, and then increases for a short time when the molecules are best aligned.
Stronger molecular alignment in our sample, as well as improved signal-to-noise ratio
in the detection of the harmonics, allowed us to observe this anomalous peak which has
not been reported previously. This feature is strongly suggestive of a phase shift due toquantum interferences.
To confirm that quantum interferences are the origin of the additional central peakin HHG from aligned molecules, we directly compare the phase of HHG from aligned
and unaligned molecules using the setup shown in Fig. 4.4. Fig. 4.7 (a) and (c) plot
the observed interference pattern for orders 25 and 31. For order 31, a fringe shift canclearly be observed when the molecules are strongly aligned. No such shift is observedfor order 27. The time window for this phase shift exactly matches the duration of theanomalous peak seen in the intensity of order 31 as a function of alignment (Fig. 4.6(d)). To determine the magnitude of the phase shift between harmonic emission from thealigned and randomly-oriented molecules, we integrate the interferences fringes between-100fs and 100fs. We then compare this with the integrated fringes outside this temporalwindow, where there is no strong alignment. The results are shown in Fig. 4.7 (b) and(d). We use a sine function added to a slowly varying polynomial background to fit thedata. We retrieve a phase difference of 3.4 ± 0.3 radians for order 31, and 0.035 ± 0.5
radians for order 27.
The inset of Fig. 4.5 (b) shows the predicted angular distribution at three different
times in the 3/4 revival, to illustrate the effect of angular averaging. As explained above,the critical angle θc corresponds to that angle where the phase of the harmonic emission
changes. At maximum alignment (red curve), most of the distribution is on one side

64

4

(a)

H21
H25
fit H21

(b)

H31
H35
fit H31

(c)

H37
H39
fit H37

Harmonic intensity (Arbitrari Unit)

2

0
6
4
2
0
6
4
2

−1000

−500

0
500
Time delay (fs)1000

Figure 4.6: Lineout of harmonic orders 21, 25, 31, 35, 37, and 39 that exhibit different
sub-structure in the harmonic emission at optimal alignment. The dashed line showsa least-square fit to Eqn. 4.6 for harmonic orders 21, 31 and 37. Figure adapted from
[55].

65

(a)

(b)

(c)

(d)

Figure 4.7: (a), (c) Interference pattern as a function of time within the 3/4 revival
for harmonic orders 25 (a) and 31 (c). (b) Intensity-scaled integrated fringes for the
25th harmonic in the -100 fs to 100 fs interval (red squares), along with least square fit(red solid line). Integrated fringes outside this temporal window are also shown (black
circles) as well as a least square fit (black solid line). (d) Same as (b), but for the 31rd
harmonic. Figure adapted from [55].

66of θc ≈ 34◦ for order 31. At the other two time delays (blue and black curve), the net
harmonic signal will have opposite phase since most of that distribution lies on the otherside of θc . Therefore, a phase shift of π is expected in the interference pattern during
the revival, in agreement with our data. In contrast, for harmonics < 27 the criticalangle is smaller, and therefore the phase of the harmonic emission does not change
during the revival. Putting this result into the context, in Ref. [48, 49] the authors
convolved the two-center harmonic intensity modulation with the angular distribution
without accounting for the coherent nature of HHG generation. Our work shows clearly
that the harmonic emission adds coherently. Other recent work [35] has also found thatto reproduce experimental data, a coherent sum of HHG emission is required to model
harmonics from aligned molecules.
From our measurements of the harmonic intensity and phase, we accurately identify the spectral position of the interference minimum and corresponding phase shift inharmonic emission, which qualitatively agree with the two-center interference model.
To further test the validity of this model, we fit the measured harmonic intensities fortimes around the 3/4 revival using the expression HHG(t) =

Z π/2

2

ρ(θ, t)A sin(πR cos θ/λ)dθ + C

(4.6)

0

In Eqn. 4.6, the sin(πR cos θ/λ) term results in quantum interference. A isa scaling factor, while C accounts for any non-coherent part in the detected signal.
Since we do not have very accurate independent measures of the rotational temperatureand the pump laser intensity, we calculate the angular distribution ρ(θ, t) for different
rotational temperatures (75 K, 85 K, 95 K, and 105 K) and pump intensities (4.0, 4.5,
5.0, 5.5, and 6.0 ×1013 W/cm2 by numerically solving the TDSE following the procedureof [57].
These values are within our experimental estimates. We performed the leastsquare fit with fitting parameters A, B (=R/λ) and C, using each one of these angular

67

1.8
E k=nhω1.6

E =nhω−I
k

p

R/λ

1.4

1.2

1

0.8

23

27

31

35

39

43

47

Harmonic orderRversus harmonic order from the fits shown in Figs. 4.6
λR(blue squares with error bar). The calculated value ofis also shown for two different
λdispersion relationships and internuclear separations: Ek = nh̄ω - Ip and R=2.32Å(blacksolid line), R=2.45Å(black dashed line); Ek = nh̄ω and R=2.32 Å (red solid line),
R=2.45 Å (red dashed line). Figure adapted from [55].
Figure 4.8: Extracted value of68
densities for all harmonic orders, and finally we sum the squares of the residuals todetermine the goodness of each fit. The best overall fit for all harmonic orders was
obtained using a rotational temperature of 105 K, and a pump laser intensity of 5.5×1013
W/cm2 . Least squares fits to Eqn. 4.6 for three representative harmonics - orders 23,
33, and 39 – are shown in Fig. 4.6. These fits are also in excellent agreement withthe two-center model, and also provide compelling evidence that the primary featuresin the angular modulation of HHG emission intensity and phase from CO2 result fromquantum interferences in the recombination process.
Since the inter-atomic separation R should be independent of the harmonic order,
we can use R as a “ruler” by which to measure the wavelength λ of the recolliding
electron [48, 61]. Fig. 4.8 plots the extracted value of B = R/λ with the error bar
determined by 95% confidence interval, together with the theoretically predicted curves
for R=2.32 Å and two different dispersion relationships: Ek = nh̄ω−δIp (0< δ <1). Our
experimental data show that the ratio R/λ does not follow a relationship corresponding
to a fixed value of δrather that δ is near 0 for low order harmonics, and increases forhigher orders. The effect of the Coulomb potential on the continuum electron is themost probable reason for this behavior. The molecular potential can further accelerate
the returning electron and distort the wave front from that of a plane wave. To a first
approximation, we can consider the Coulomb effect as a correction to the kinetic energyof the returning electron plane wave. The equation Ek = nhω - Ip gives asymptotic
kinetic energy of the electron, corresponding to some momentum vector k.
Further acceleration of the electron inside the molecular potential will give anadditional momentum shift ∆k and a phase shift∆k · R. Our data show that this phaseshift is small for high order harmonic and larger for lower orders. For harmonic orders
below 25, our extracted value of Ek = nh̄ω is even larger than the calculated value
using a dispersion relationship Ek = nh̄ω, which most likely is due to a breakdown of
the plane wave approximation for low order harmonics. Other possible explanations

69
include multi-electron effects, or field distortion of the molecular HOMO which might
stretch the effective distance between the centers of electron density. Two dashed curves
calculated using a slightly longer R (2.45 Å) are also shown in Fig. 4.8 for comparison.
The effort to develop a complete theory of HHG in molecules that includes multi-electron
and Coulomb effects will be helpful to fully understand our data [39, 62, 40, 63].

4.5

Quantum interference in N2 O and N2 molecules
N2 O is a linear molecule with a HOMO structure very similar to CO2 . Becauseof the asymmetry of nitrogen and oxygen atoms, N2 O has a permanent dipole moment.
However, the orientation effect is averaged out during the pump pulse, therefore, we
observe similar behaviors of HHG from aligned N2 O and CO2 molecules. The HHG
intensity evolution during a full rotational period of N2 O is shown in Fig. 4.9, Due todifferent nuclear spin statistics, N2 O molecules do not have strong 1/4 and 3/4 revivals
as in the case of CO2 .
There is a local maximum when the molecules are strongly aligned for harmonicorder above 27. This local maximum corresponds to the two center interference induced
phase flip. We perform a double-foci interferometry measurement as shown in Fig. 4.10
for harmonic orders 25 and 29, the π phase change is clearly visible for harmonic 29th
when the molecules are aligned.
There is an extra feature for low order harmonics (15th, 19th, and 23rd), when themolecules are anti-aligned. This local minimum on the top of the anti-alignment peak
can also be explained by the two-center modulation factor shown in Fig. 4.3. Because
when the molecules are anti-aligned, the angular distribution can pass the peak of themodulation factor and start to decrease. The angle where this peak located is small for
low order harmonics, therefore, easy to be achieved.
We also extend our interferometry technique to N2 molecules. Unlike N2 O and

70

3

H15
2
1
0
0
10

5

10

15

20

25

HHG intensity (Arb. Unit)

35

40

45

35

40

45

35

40

45

35

40

45

35

40

45

35

40

45

H19

5

0
60

30

5

10

15

20

25

30

4
2
0
0
3

H23
5

10

15

20

25

30

H27

2
1
0
0

5

10

15

20

25

30

1.5

H31
1
0.5
0
0
0.5

5

10

15

20

25

0.4

30

H35

0.3
0.2
0.1
0
0

5

10

15

20

25

30

Time delay (ps)Figure 4.9: Measured harmonic intensity for the 15th, 19th, 23rd, 27th, 31st, and 35th
harmonics during a full rotational period of N2 O.

71

40

H25

35
30
25
20
15
10

CCD pixels

5

40

H29

35

30

25

20

15

10

5

Time delay during half revival
Figure 4.10: Interference fringes as a function of time delay during half revival for the
25th (a) and 29th (b) harmonics from N2 O.

72
CO2 , the HOMO of N2 can not be decomposed to pure ‘+’ or ‘-’ sign superpositionsof atomic orbitals. The N2 molecular orbital is constructed by a mixture of 70% of
atomic p orbitals and 30% of atomic s orbitals. The atomic p orbitals are superposedwith a ‘-’ sign and the atomic s orbitals are superposed with a ‘+’ sign. The HOMO
of N2 has a σg symmetry. Consequently, two-center interference model are not enoughto describe the alignment-dependent HHG emission from N2 . Under the plane-wave
approximation, we can calculate the HHG dipole by performing Fourier transform of
the molecular HOMO calculated with quantum chemistry code. These calculations arecarried out in two recent papers [64, 65]. Both calculations predict a π phase jump at
the harmonic range and alignment angles that are experimentally accessible, although
the exact location of this phase jump slightly depends on how HOMO wave function
is calculated. However we do not see any angle dependent minimum and phase change
in our measurement of N2 during the revivals, as shown in Fig. 4.11. We perform thephase measurement on N2 as well, we do not see any phase shift for harmonic orders
between 19 and 33.
In summary, for CO2 and N2 O molecules, we present an accurate and unambiguous measurement of the phase shift of high-order harmonic emission in molecules forthe first time. The data also allow for a detailed measurement of the dispersion relation
between the wavelength of the recolliding electron and the harmonic order. While forN2 molecules, we do not observe the angular dependent phase shift and minimum predicted by the plane-wave recombination model. Therefore, our data will be very useful
to benchmark complete theories of harmonic emission from molecules.
A recent experiment [66] also measures the angular dependent harmonic phaseof CO2 using the interference of two-photon (one EUV photon and one IR photon)transitions [67].

73

4000

500000400000HHG intensity

3000

Harmonic 21

Harmonic 45
3000002000

2000001000

100000
0

0
-1000

0

2000

4000

6000

8000

10000

80000

12000

0

2000

4000

6000

8000

10000

50000

12000
37

70000
40000

HHG intensity

60000

Harmonic 29
50000

30000

Harmonic 37

40000
20000
30000

20000

10000

10000
0
0

-10000-10000

0

2000

4000

6000

8000

Time delay (fs)

10000

12000

0

2000

4000

6000

8000

10000

12000

Time delay (fs)Figure 4.11: Intensity change versus time delay during a full rotational period of N2 .

Chapter 5

Polarization resolved characterization of HHG from aligned molecules

5.1

Observation of elliptically polarized HHG from molecules
driven by linearly polarized laser light
In principle, the amplitude, phase and polarization of the HHG emission can bemeasured and used to extract the electronic structure of molecules from the transition
dipole matrix element. However, until very recently, only the intensity of high harmonic
emission was measured. Fortunately, new approaches have allowed the phase of HHG
to be determined as we discussed in the last chapter [55, 66].
In this chapter, we perform a full and accurate polarization measurement of highharmonic emission from aligned molecules for the first time. Surprisingly, we find that
harmonic emission from nitrogen molecules can be strongly elliptically polarized evenwhen driven by linearly polarized laser fields. We extract the relative phase difference
between the HHG components parallel and perpendicular to the driving laser field,
which depends only weakly on molecular alignment but which strongly depends on theharmonic order. Our findings differ from previously published results [68], where only
linearly polarized harmonic emission was observed, because we achieve stronger molecular alignment and better signal-to-noise ratio (∼1% intensity fluctuation), allowing us
to detect an elliptically polarized HHG emission when molecules are driven by linearlypolarized laser fields. These findings cannot be explained by a plane wave SFA, andwill be very useful to benchmark new and more complete theories of molecules in strong

75
fields. Moreover, our results present a straightforward and efficient way to generate
circularly polarized harmonic beams for applications in molecular and materials science.

The polarization state of harmonic emission from molecules is especially interesting for the following reasons. As shown in Fig. 5.1 (a), in general, the complex amplitudeof the harmonic field from a molecule has two components, parallel (y) and perpendicular (x) to the laser polarization respectively. Any component along the laser propagation direction cannot be phase matched. Ey (ω, θ) = |Ey (ω, θ)| exp(iΦy (ω, θ)) andEx (ω, θ) = |Ex (ω, θ)| exp(iΦx (ω, θ)) depend both on the harmonic frequency ω and angle θ. In theory we should get the same reconstruction of the molecular orbital from bothof the HHG components [70]. Moreover, according to the 3-step model, the ratio between
the x and y components can be written as |Ex (ω, θ)/Ey (ω, θ)|2 = |dx (ω, θ)/dy (ω, θ)|2 ,which is independent of the angle-dependent ionization and is directly related to thetransition dipole in these two directions. In this way, the ionization and recombination
process in HHG can be isolated and studied separately. Finally, from the polarization
properties of the HHG emission (the orientation angle φ and the ellipticity ǫ as definedin Fig. 5.1 (b)), we can map out the relative phase difference δ = Φx − Φy between thex and y components. Again, because the ionization and acceleration steps are common
for the x and y components of HHG, this relative phase difference is not entangled with
the intrinsic phase accumulated while the electron oscillates in the continuum. Thus,
measuring the polarization properties of HHG should allow clear insight into strong field
molecular science and also enable critical comparison with theory.
In our experiments, pump and probe pulses from a two-stage Ti: Sapphire amplifiersystem are focused (non-collinearly) into a molecular gas. The pump pulse is focusedby a 75 cm lens to an intensity of 4∼5 × 1013 W/cm2 , and is used to create a rotational wave packet and field-free alignment in the molecular sample. The probe pulse
is focused using a 40cm lens to an intensity of 2×1014 W/cm2 and generates harmonics

76

(a)

(b)

θ

y

HHG EyAligning pump laser

φ χ

γ

x
HHG ExHHG probe laser
HHG Ellipse
Figure 5.1: High harmonic generation from aligned N2 . (a) HHG components paralleland perpendicular to the probe laser polarization can be generated. The angle γ isdefined by tan(γ)= |Ex |/|Ey |. (b) The orientation angle φ of the HHG ellipse is definedas the angle between the major axis of the ellipse and the y axis. The angle χ is definedby tan(χ)=ǫ, where ǫ is the ellipticity. φ and θ are positive for clockwise rotation fromthe y direction and negative for counter-clockwise rotation. Figure adapted from [69].

77from the aligned molecules. Both foci are positioned ∼150 µm from a supersonic gas
jet, with a 150um orifice diameter and 700∼800 Torr backing pressure. The rotationaltemperature of the gas was estimated to be 100 K and cos2 θ is estimated to be 0.65
when the molecules are aligned. This high degree of alignment improves the measurement precision compared with past experiments, allowing us to observe a strong HHG
component perpendicular to the laser polarization. Both alignment and harmonic generating pulses are linearly polarized. A computer controlled half-wave plate (HWP1) in
the alignment beam controls the relative angle θ between the polarization of the pumpand probe, while a second half-wave plate (HWP2) in the common path of the pumpand probe beams can rotate the polarization of both beams together.

5.1.1

Experimental setup

To measure the polarization of the harmonic emission, the HHG beam was reflected from two gold mirrors (consisting of a gold layer of 250 nm coated on a superpolished substrate) at an incident angle of 45◦ . These mirrors act as an EUV polarizer,
selectively reflecting S-polarization. The HHG beam was spectrally separated using an
EUV spectrometer (containing a grazing incidence cylindrical gold mirror and EUV
grating) and finally detected using an EUV CCD camera (Andor Technology). The
transmission of the EUV spectrometer weakly depends on the incident light polarization. Due to the decreasing reflection efficiency of the gold mirrors at shorter wavelengths, only harmonic orders below the 31st can be observed. The intensity extinction
ratio e of the entire detection system is carefully measured using HHG generated fromisotropic molecules and atoms: e monotonically decreases from 0.08 at harmonic order 13, to 0.005 at harmonic 31. Note that the HHG beam can be partially polarized
due to spatial and temporal variation of the HHG field [71]. Thus the extinction ratio measured could be contaminated by any unpolarized HHG emission. However, theDAQ computerGold coated flat mirror

HWP 1

HWP 2

CCD

Figure 5.2: Setup for measure the polarization of HHG from aligned molecules and the reflectivity of a gold-coated mirror for S and P
polarized light.

78

79
measured extinction ratio e is consistent with the calculated value for the gold mirrors
pair based on optical constants, within a error of 0.015 for all harmonic orders observed[72]. Thus, we conclude that the harmonic emission is almost fully polarized and thatthe HHG ellipse parameters (φ and ǫ) are constant temporally and spatially [71]. Thus,in this paper we neglect the effect of unpolarized HHG.
If the polarizations of the pump and probe beams are parallel, the molecular angular
distribution is cylindrically symmetric around the laser polarization. Thus, harmonic
emission is always polarized along the laser polarization direction. To investigate thepolarization of the harmonics as a function of molecular orientation, we varied the angle
between the aligning pump laser and the HHG-generating probe pulse (see Fig. 5.1),
while fixing the time delay corresponding to a full revival for N2 and a three quarters
revival for CO2 such that the molecules are strongly aligned. When the cylindrical symmetry around the HHG driving laser polarization is broken, a component of harmonic
emission that is perpendicular to the driving laser polarization should be observable
experimentally.

5.1.2

Intensity ratio between the parallel and perpendicular components

We first analyze the intensity ratio between the parallel and perpendicular components of harmonic emission as a function of angle θ. The ratio between the measured
HHG intensity when the harmonic generating laser is parallel and perpendicular to thetransmission axis (S polarization) of the EUV polarizer is equal toeIy (θ) + Ix (θ)
whereeIx (θ) + Iy (θ)

Ix (θ) = |Ex (θ)|2 and Iy (θ) = |Ey (θ)|2 . Since eIx (θ) ≪ Iy (θ), subtracting the measured
e from this ratio gives the true intensity ratio between the y and x components. The
intensity ratios for N2 and CO2 molecules are plotted in Figs. 5.3 (a) and (b) for different harmonic orders and relative angles. For N2 , we obtain zero values of this ratiofor θ =-90◦ , 0◦ , and 90◦ , which confirms the accuracy of our background subtraction

80

(a)

(b)

Figure 5.3: Ratio between the perpendicular (x) and parallel (y) components of the
HHG field Ix (θ)/Iy (θ) (a) for N2 (a) and (b) for CO2 molecules. Figure adapted from
[69].

81
procedure. For CO2 , these values can slightly go below zero due to fluctuations, since
the intensity of the perpendicular component is smaller compared with N2 . Comparing
the intensity ratios of the HHG polarization components for N2 and CO2 shown in Fig.
5.3, we can clearly see differences. The ratio for N2 is peaked at harmonic order 23. For
CO2 however, the ratio decreases between harmonic orders 15 and 21, but then increases
quickly for harmonic orders above 23. This is because for harmonics around the 27th,
the y component reaches a minimum due to two-center interference effects [9], which
also makes an accurate ratio measurement difficult. The polarization properties of theharmonic emission do not only depend on the amplitudes of the x and y components,
but also their relative phase difference δ. If δ is 0 or π, the HHG emission will still belinearly polarized, but the nonzero perpendicular component Ex will rotate the HHG
polarization away from the driving laser polarization direction by an angle given byarctan(|Ex |/|Ey |). For other values of δ between 0 and π, the HHG will be ellipticallypolarized, and the orientation angle φ will be less than arctan(|Ex |/|Ey |). Particularly,for δ =π/2 the major axis of the HHG ellipse will be in the direction of the driving laser
polarization.

We also measure the temporal evolution of the perpendicular HHG component
during a full rotational period of N2 (Fig. 5.4), when the angle between the pump andprobe pulse is 45◦ .

5.1.3

Orientation angle

To implement a full polarization characterization, we rotate the relative angle θ
between the pump and probe from -90◦ to 90◦ , in 10◦ steps. Although the intensity
transmission of an elliptical polarized beam through an imperfect polarizer (e >0) can

82

Figure 5.4: The temporal evolution of the perpendicular HHG component during a fullrotational period of N2 .

83
be described by a more sophisticated formula containing Ix , Iy and e as parameters,qI(α) = (1 + e)(Ix + Iy )/2 + (1 − e) cos(2(α − ϕ)) Ix2 + Iy2 + 2Ix Iy cos(δ)/2(5.1)

we prefer to use fewer fitting parameters and to extract these values from the final fitting
result.
For each pump-probe angle, we rotate the second wave plate (which rotates thepump and probe polarizations together) by 360◦ , in 4◦ steps. We then fit the polarimetry scan data using the formula I(α) = a×cos[2(α−φ)]+c, where α is the angle between
the polarizer transmission axis and probe laser polarization. For each polarimetry scan,
the maximum and minimum positions correspond to the orientation angles of the major
and minor axes of the HHG ellipse.

Figure 5.5: Interpolated color map of the orientation angle φ in degrees for different
harmonic orders and molecular orientations for (a) N2 and (b) CO2 . The HHG ellipse
at θ=50◦ for harmonic orders 13-27 is also illustrated. Straight lines represent theharmonic polarization in CO2 since the ellipticity is small. Figure adapted from [69].

The extracted orientation angle φ of the HHG ellipse in the case of N2 is plottedin Fig. 5.5(a). For harmonic orders below 19, the major axis of the HHG ellipse rotatesin the same direction as the molecular axis, while for harmonic orders greater than 19,
the major axis rotates in the opposite direction to the molecular axis. The change oforientation angle of the HHG ellipse is up to 20◦ , indicating that a stronger molecular

84alignment was achieved in our sample than was the case in previous work [68]. As shownin Fig. 5.3 (a), a strong perpendicular component for the 19th harmonic was observed.
However, since the orientation angle of this harmonic stays in the same direction as
the HHG driving laser polarization, (φ ≈ 0◦ for the 19th harmonic in Fig. 5.5(a)), thisharmonic must be elliptically polarized.

However, for elliptically polarized light, the ratio between the minimum andmaximum transmitted intensity of the polarimetry scan Imin (θ)/Imax (θ) is given by
Iminor + eImajor
Iminor≈ e+
and Imajor are the intensity of the minor and major axis
Imajor + eIminor
Imajorof the HHG ellipse. Therefore, the ellipticity of the harmonic emission, defined as ǫ(ω,θ)= , can be extracted from the polarimetry measurement, and is shown in Fig. 5.6 (a).
We find that harmonics from aligned N2 molecules can be strongly elliptical polarized,with ellipticity up to 0.35 for harmonic orders near the 21st. The extracted ellipticity
ǫ for different harmonic orders at orientation angles θ=40◦ , 50◦ and 60◦ are plotted inFig. 5.6 for N2 (these data are averaged for positive and negative θ angles). In contrast,
for CO2 , the measured ellipticity is relatively small (<0.1), which is a few times smaller
than in the case of N2 and only slightly above the noise fluctuation. Thus, the strong
perpendicular components at harmonic orders below 17 and above 23 shown in Fig. 5.3(b) rotates the predominantly linearly polarized HHG without introducing significant
ellipticity. As shown in Fig. 5.5 (b), this rotation of the polarization is in the opposite
direction to the rotation of the molecular axis.

5.1.4

Ellipticity and phase delay

From the measured ellipticity ǫ and orientation angle φ of the N2 harmonic fieldpolarization ellipse, we can extract the phase difference δ between the polarization components, using the formulae sin(2χ)=sin(2γ)sin(δ) and tan(2φ)= tan(2γ)cos(δ) [73].

85
o

40
50 o
60 o

0.4

Ellipticity ε

0.35
0.3
0.25
0.2
0.15
0.1

13

15

17 19 21
Harmonic Order

23

25

27

15

17
19
21
Harmonic Order

23

25

27

1
Phase difference δ (unit π)

40 o
50 o
0.8

60

o

0.6

0.4

0.2

13

Figure 5.6: (a) Ellipticity ǫ for relative angles between the pump and probe of θ =40◦ ,50◦ and 60◦ , as a function of harmonic order for N2 . (b) Calculated phase difference
δ between the parallel and perpendicular components of HHG emission in N2 . Figure
adapted from [69].

86
The extracted value of δ for θ=40◦ , 50◦ and 60◦ degrees for different harmonic orders
is plotted in Fig. 5.6 (b) for N2 . The relative phase difference is almost independent of
the molecular orientation angle θ, and gradually increases from 0.2 π to 0.8 π between
harmonic order 13 and 27. For harmonic order 19, the relative phase δ is nearly π/2.
(Since we do not measure the handedness of the beam, there is an ambiguity in the signof δ.)As pointed out in [68], for a plane wave recombination dipole, the phase difference
between the y and x components of the harmonic emission is either 0 or π. Thus, the highharmonic emission should be linearly polarized. Moreover, the position of any phasejump arising, for example, from a quantum interference effect should depend on themolecular orientation angle. Using a recently demonstrated molecular interferometry
technique to measure the phase of the harmonic emission from N2 during a rotational
revival with parallel polarized pump and probe beams, we found that the phase of theharmonic emission from N2 does not depend on orientation of the molecule, and that
there is no angle-dependent intensity minimum for harmonic orders 19 – 31. Therefore,
the observed significant but smooth variation in relative phase difference over 8 harmonicorders cannot be fully explained by assuming a plane wave recombination dipole. Our
results possibly indicate a breakdown of the plane wave approximation, which could
result in a delay between the oscillating dipole in the y and x directions. In principle,
both the signature of the HOMO on the ionized electron wave packet and the influenceof the Coulomb potential on the recombination process could generate a phase delay
between the dipoles corresponding to the two components of polarization [74]. The
significant difference between N2 and CO2 molecules clearly are related to their different
molecular orbitals. The contribution from the lower-lying molecular orbitals is anotherpotential reason for the observed ellipticity [63]. Thus the observed HHG ellipticity inN2 may reflect nontrivial electronic dynamics.

87
In summary, we have uncovered unexpected polarization properties of high harmonic emission from N2 and CO2 molecules that have broad implications for the theoryof molecules in strong fields. First, we found that elliptically polarized harmonics canbe emitted by molecules and that the relative phase between the y and x componentsof the harmonic field strongly depends on the harmonic order.
Second, although N2 is a simple diatomic molecule and was used for molecular
tomography experiments, the 3-step model cannot completely describe the behavior of
harmonic emission from N2 . Combined with recently developed techniques for measuring the phase of HHG from molecules [55, 66], we have made a significant step forward
in a complete characterization of harmonics from simple molecules. For N2 , as discussed
in the previous chapter, the phase of the parallel component does not depend on themolecular orientation. Although it is difficult to make a direct measurement of thedependence of the phase of the perpendicular HHG component on the molecular orientation due to the small flux, it would be surprising if the phase of the perpendicularcomponents depend on the molecular orientation. Since our measurement show thatthe relative phase between the parallel and perpendicular HHG component depends
on the harmonic order N2 , we conclude that the recombination phases of parallel andperpendicular HHG components of N2 depend on the harmonic order in a complex way,
but these phases do not depend on the molecular orientation.
Finally, our results present a straightforward and efficient way to generate circularly polarized harmonic beams for applications in molecular and materials science.

5.2

Polarization-resolved characterization of HHG emission fromaligned molecules with elliptical polarized fundamental light
HHG from atoms with elliptical polarized driven laser have been studied inten-

sively [75, 76, 77, 78]. The ellipticity of the fundamental laser can steer the electron wave
packet, which causes a lateral shift of the return electron wave packet away from the88parent ion and reduces the probability of recombination. The HHG yield decays very
quickly with the increasing ellipticity of the driven laser, and usually, the fundamental
ellipticity dependence of HHG is a Gaussian shape and centers at zero ellipticity. Ref.
[79] attributed the observed deviation from Gaussian shape of the threshold harmonics
to the interaction of the ionized electron with the Coulomb potential. The ellipticity
can also change the trajectory and recollision angle of the electron in the continuum.
The harmonics generated by an elliptical polarized fundamental IR laser also havea complicated polarization state, due to the existence of a perpendicular component andthe nontrivial phase between the perpendicular and parallel components. A previous
measurement revealed that the HHG was elliptically polarized and that the long axisof the polarization rotates away from the long axis of the fundamental laser ellipse[80, 81, 71]. The direction of this rotation depends on the harmonic order.
The ellipticity dependence of the HHG has been used recently for generating asingle attosecond pulse with polarization gating techniques [82, 83], where a fundamental
laser pulse with time-dependent polarization was used to generate harmonics. A few
laser cycles in the center of the pulse have linear polarization, which generate harmonics
efficiently. The time-dependent polarization gradually becomes circular on the leading
and trailing edge of the pulse, where the HHG yield is suppressed.
The trailing and leading edges of the generated EUV pulse are generated bya slightly elliptically polarized fundamental laser, therefore, they are not linearly polarized. It is interesting to characterize the perpendicular and parallel components
separately of these pulses. Thus we can evaluate the importance of the perpendicular components when we apply the attosecond pulses generated by polarization gating
techniques to polarization-sensitive applications such as photoelectron spectroscopy.
Some experiments have tried to measure the fundamental laser ellipticity dependence of the HHG from aligned molecules. The ellipticity dependence of HHG from
CO2 and N2 has been measured for two special cases, aligned or anti-aligned molecules

89
in Ref. [84]. Y. Mairesse et. al. [85] performed a more general measurement for several
angles between pump and probe (long axis of the polarization ellipse) polarizations.
In this section, we present a polarization-resolved measurement of HHG fromatoms and aligned molecules generated by an elliptically polarized laser light. Our
elliptical polarized fundamental light is generated by a combination of a rotatable halfwave plate and a fixed quarter-wave plate. The long axis of the fundamental ellipse
remains along the S polarization of the gold mirror polarizer when the HHG component parallel to the long axis of the fundamental ellipse is measured; and along the P
polarization of the gold mirror polarizer when the HHG component perpendicular tothe long axis of the fundamental ellipse is measured.
We present the data for fundamental ellipticity dependences of the perpendicular(⊥) and parallel (k) HHG components of Ar, and N2 . For the parallel HHG component
from Ar, we observe same behavior as in Ref. [86] that the higher order harmonics
decrease faster with increasing ellipticity than low order harmonics. As shown in Fig.
5.7, there is no perpendicular HHG component at zero ellipticity. The perpendicular
HHG components are maximized at a nonzero ellipticity, and further increasing of theellipticity will finally decrease the HHG yield.
For N2 molecules, if the angle between the pump and probe polarization is neither0◦ nor 90◦ , as shown in Figs. 5.8 and 5.9, we observe that both parallel and perpendicular
HHG components do not peak at linear polarization of the driving laser, but rather peakat a small positive or negative ellipticity. The sign and magnitude of this ellipticity
depend on the molecular orientation. An interesting feature is that the sign of thisellipticity is opposite for parallel and perpendicular HHG components. For example,
when the angle between pump and probe pulses is -50◦ , the maximum of the parallel
component of the 15th harmonic is located at a slightly negative ellipticity, -0.017,
similar to the result of [85]. While the maximum of the perpendicular HHG component
is located at a much larger positive ellipticity 0.08.

90

0.7

HHG intensity (Arb. Unit)

0.6
0.5
0.4
0.3
0.2
0.1
23
0

0.2

0

17
−0.2

−0.4

−0.6

−0.8

rm

on

ic

19
0.4

Ha

−0.1
0.6

or

de

r

21

15

Probe laser ellipticity

Figure 5.7: Perpendicular HHG components from Ar atoms for harmonic order 15-23
versus the fundamental ellipticity.

91

(a)

15th

(b)

21st

Figure 5.8: 2D color map of parallel HHG components of 15th (a) and 21st (b) harmonics
from N2 molecules as a function of the fundamental laser ellipticity and molecularalignment angle. These data have been normalized to the maximum value of eachharmonic.

92

Figure 5.9: 2D color map of perpendicular HHG component of 21st harmonic from N2
molecules as a function of the fundamental laser ellipticity and molecular alignment
angle.

93
In summary, the HHG from aligned molecules using an elliptical polarized driven
laser offers more information than the HHG using a linearly polarized laser. However, tofully understand the data of these experiments, a more sophisticated model is required.

Chapter 6

Real Time Monitoring of Molecular Dynamics with HHG

The experiments discussed in the last two chapters have confirmed the sensitivity of HHG to the static electronic structure of aligned molecules. Scientists are alsointerested in studying the dynamics of molecules with HHG. The attosecond time-scale
electron recollision process that underlies high harmonic generation shows great promise
as a probe of molecular dynamics, particularly so if it can be applied to complex polyatomic molecules.
Recently, two experiments were performed to investigate the effects of nuclear
motion on HHG. Baker et al. studied the harmonic generation from H2 and D2 molecules[87]. They showed that the ratio between the HHG from H2 and D2 molecules depends
on the harmonic order, which can be explained by the faster nuclear motion of the
protons in H2 during the ionization and recombination events of HHG. The recollison
electron acts as the probe for the nuclear motion, that is initiated by the ionization.
The different recollision times for different harmonic orders serve as the pump probe
time delay.
We performed another experiment on SF6 molecules, which is more similar tothe conventional pump probe experiments. In this effort, we used the pump pulse
to excite the vibration motion in SF6 molecules through impulsive stimulus Ramanprocesses, which excited three of six Raman active modes in the SF6 molecules [88].
The modulation of the HHG yield was small in this experiments and the result can be

95
explained by vibrational wave packet beating [89].
In this chapter we show that high harmonic generation can reveal coupled electronic and nuclear dynamics in polyatomic molecules [90]. By exciting large amplitude
vibrations in the N2 O4 , we show that tunnel ionization accesses the ground state of theion at the outer turning point of the vibration, but populates the first excited stateat the inner turning point. This state switching mechanism is manifested as brightbursts of high harmonic light emitted mostly at the outer turning point of the vibration. Theoretical calculations attribute the large modulation to suppressed emission in
the first excited state of the ion. More broadly, the result imply that high harmonic
generation and strong field ionization in polyatomic molecules undergoing bonding or
configurational changes involve participation of multiple molecular orbitals

6.1

Vibration in N2 O4
In polyatomic molecules, electronic and vibrational excitations can couple anddynamically redistribute both energy and charge during dynamic processes. Due tothe importance of these dynamics in chemical and biological systems, the capability
to probe dynamics in large polyatomic molecules is ultimately a requirement for any
broadly useful spectroscopy or dynamical imaging technique. Time-resolved photoelectron spectroscopy (TRPES) is a weak field (perturbation regime, laser intensity<109
W/cm2 ) method that can uncover these dynamics [27, 91, 92]. In TRPES, the molecule
is first excited by a pump pulse. A time-delayed probe pulse then projects the complex
evolving wave packet onto the molecular ionization continuum, and the outgoing electron is analyzed as a function of pump-probe delay. The cation electronic states andtheir associated electronic continua, and the vibrational structure of the ionization continuum, are both used as a ‘templates’ for projecting out the electronic and vibrational
components of the complex wave packet. This evolving projection onto multiple elec-

96tronic continua permits the disentangling of electronic and vibrational dynamics during
non-adiabatic processes in polyatomic molecules [93].
High harmonic generation (HHG) is a strong field (non-perturbation regime, laser
intensity >1012 W/cm2 ) process [94, 95]that is closely related to photoelectron spectroscopy. In atoms, HHG is successfully described by an adiabatic, single active electron(SAE) model involving three steps: strong-field tunnel ionization, propagation of thecontinuum electron in response to the laser field, and finally recombination of the electron with its parent ion resulting in emission of a high energy photon [12, 13, 14].
However, in the case of HHG from a polyatomic, the physics is more complex due tothe many-body electronic structure of polyatomic molecules and the existence of rovibrational and non-adiabatic dynamics. The recombination matrix element for the
HHG process and the photoionization matrix element of the photoabsorption process
are the same since these steps are inverse to each other. Therefore, the multiple electronic continua relevant to probing complex polyatomic dynamics via TRPES must also
play a role when HHG is used to probe these dynamics. The use of HHG as a probe has
two potential advantages over TRPES: first, the ability to access attosecond time scale
processes, and second, the ability of HHG to simultaneously probe with many photon
energies. However, until recently, only the highest occupied molecular orbital (HOMO)
has usually been considered to explain both strong field ionization and high harmonic
emission. This simplification comes from the adiabatic and single active electron approximations that underlie theories of tunnel ionization in atoms and molecules (ADKand molecular ADK) [18, 26]) and that are integral to the three-step model of HHG[12, 13]. In polyatomic molecules however, both approximations can fail dramatically- particularly so when the molecule is dynamically evolving, as we show in this work.
Strong field ionization can become both non-adiabatic and involves multi-electron excitations [96, 97]. Theoretical efforts to relax the single active electron approximation
are being attempted in order to address this issues by introducing multi-electron effects

97
in the recombination step of HHG [39, 98].

Past work has investigated HHG from rotationally aligned molecules as a potential probe of static molecular structure [37, 55], since the emission strength depends
on the molecular orbital nature of the ground electronic state and its alignment withrespect to the laser field. Recent, related work has also used the photoelectrons released
and rescattered during the strong field ionization process to recover the static orbital
structure of simple diatomic molecules [99]. High harmonic generation also has beenused as a probe of simple dynamics in molecules where, for example, the molecular
structure was slightly changed without any bond reorganization. Past work has shownthat the high harmonic generation process is sensitive to simple vibrational dynamics
in a molecule, even to modes that cannot readily be probed optically [88, 89]. The
rearrangement of atoms within a molecule during the HHG process can also be inferredby comparing HHG spectra of isotope-substituted molecules [87]. Chemical dynamics,
however, involve large amplitude motions. HHG experiments have yet to succeed inobserving and understanding large-amplitude structural rearrangements within a polyatomic molecule, where the simple assumptions are unlikely to remain valid because ofdramatic and evolving changes in the ionization/recombination dynamics.
Here we successfully apply high harmonics generation as a time-resolved probe ofchemical dynamics in a polyatomic molecule. By exciting a large amplitude vibrational
wave packet motion in the ground state of a dinitrogen tetraoxide (N2 O4 ) molecule,we observe large modulations in harmonic yield. We discover that at the outer turning
point of the vibration, tunnel ionization populates the ground state of the ion (HOMO+
Ag continuum), which has a large recombination dipole and therefore a high probability
for harmonic emission. In contrast, at the inner turning point, the first excited stateof the ion is populated by tunnel ionization (i.e. the (HOMO-1)+ B2g continuum).
This channel has a small recombination cross-section and thus suppresses the harmonic

98emission.

6.2

HHG probing of N2 O4 dynamics
N2 O4 is a dimer of NO2 , with a dissociation energy of ∼0.65 eV. N2 O4 can bepresent in significant quantities (80%) even at room temperature. The molecule has
D2h symmetry and six Raman-active vibrational modes, the strongest being the low
frequency N-N symmetric stretch (265 cm−1 , 0.03eV). By non-resonantly exciting thismode via impulsive stimulated Raman excitation (ISRS), we can generate a large amplitude ground state vibrational wave packet along the N-N coordinate. This large
amplitude motion samples a broad range of ionic configurations, leading to the participation of more than one molecular ionization continuum in the HHG process, as
illustrated in Fig. 6.1.
In our experiment, ultrashort laser pulses from a Ti: Sapphire laser system (800
nm, ∼30 fs, 4 mJ, 1 kHz) are split into pump (25%) and probe (75%) pulses. The pumppulse is focused onto a N2 O4 gas jet (backing pressure ∼700 torr) at an incident intensity of 2 x 1013 W/cm2 , to impulsively excite ground-state vibrations in the molecule.
The time-delayed probe pulse is focused to an intensity of ∼2 x 1014 W/cm2 to generate high harmonics from the vibrationally excited molecules. The relative polarizationsof the pump and the probe pulses are controlled using a half-wave plate in the pumpbeam path. The generated harmonics are then spectrally separated using a EUV spectrometer (Hettrick Scientific) and imaged onto an EUV-sensitive CCD camera (Andor
Technology). The ion signal can also be collected using a mass spectrometer.
Fig. 6.2(A) shows the experimentally observed high harmonics, from orders 19 to
27, as a function of pump-probe time delay. Lower order harmonics were not observed
because of absorption by the 0.2 µm thick aluminum filter used to reject the pumplaser light. Even in the raw data, a time-dependent oscillation of the harmonic yield

99

Pump beam

Focusing
lens

Beam Splitter

Harmonic Order

Probe beamGas jetHigh harmonics
from vibrating N2O4

Time

EUV grating
Aluminum Foil
EUV mirror
High harmonics

A

EUV camera

Strong HHG Electron

Weak HHG

recombination

Electronrecombination(HOMO-1)+

Ionization

Ionization

Energy(HOMO)+

Vibration
N2O4

N-N Bond Length
B
Figure 6.1: (A) Experimental setup. N2 O4 molecules from an effusive nozzle are excited and probed using ultrafast 800 nm laser pulses. The pump pulse intensity andduration are chosen to impulsively excite, but not ionize or dissociate, N2 O4 . A more
intense, collinear, probe pulse (2 x 1014 W/cm2 , 30fs) generates harmonics from thevibrationally-excited dimer. (B) Schematic of the experiment showing potential energy
curves for N2 O4 as a function of N-N bond length. Figure adapted from [90].

100
is apparent. For all the harmonic orders observed, the time dependence of the HHG
emission(Fig. 6.2(C)) shows several common characteristics: a sudden drop in HHG
yield when the sample is initially excited at time-zero, followed by strong oscillations in
the HHG yield imposed on a slowly rising baseline. The strong suppression of harmonic
generation at time zero is a result of coherent effects due to the overlap of the pumpand probe. Strong oscillations in the harmonic yield are present for both parallel andperpendicular polarizations of the pump and probe (Fig. 6.2).
The origin of the strong oscillations in the harmonic yield becomes apparent if we
apply a discrete Fourier transform to these data. A single peak at 255±10 cm−1 appears
in the transform spectra (Fig. 6.2 (C), 6.2 (D) inset). This frequency corresponds
unambiguously to the Raman active 265 cm−1 N-N stretch mode of N2 O4 . Given the
ISRS pump mechanism employed here, the initial motion of the vibrational wave packet
will be repulsive, with the outer turning point occurring one quarter period after thepump pulse. To verify the exact timing of the emission, we used argon gas in the same
setup, since HHG from Ar exhibits a transient only at time-zero due to coherent effects.
We thus verified that in N2 O4 , a large peak in HHG yield appears at 170±10fs—in very
good agreement with T+T/4 (T=130fs: vibration period) for the N-N stretch modeof N2 O4 . This timing clearly indicates that harmonic yield peaks at the outer turning
point of the N-N stretch vibration. The first peak in emission at T/4 (∼35 fs) is lessobvious, likely due to pump-probe overlap that suppresses the signal.

6.3

Monitoring the ionization yield
We also measured the ionization yield as a function of pump-probe delay (seeFig. 6.3). The yield of N2 O4 + is approximately the same at the inner and outerturning points. This finding shows that at the inner turning point, the molecule isionized but harmonic emission is suppressed. Hence, ionization alone (i.e. modulation

101

(A)

(B)

1.2

0.8

1
23
0.9

0.4
23

21

í1000

19

0
1000
Time
delay
(fs

)

ic
on

rm
Ha

17
2000

r
de
or

0
-1000

T/4

T/4+T

15

r
de
or

rm
Ha

1.2
Normalized Flux

1.0
0.9

FFT Amplitude (arb.)

Normalized Flux

17
2000

ic
on

(D)

1.1

0.8
0.7
0.6
-1000

19
0
1000
Time delay (fs)

15

(C)
1.2

21

1.0
0.8

255cm-1

0.6

0.8
0.6
0.4

0.4
0.2

0.2

0.0
150

300

450

Frequency (cm-1)0

1.0

FFT Amplitude (arb.)

HHG Yield

1..5

1000

Time delay (fs)

2000

600

3000

0
-1000

1.0
0.8

255cm-1

0.6
0.4
0.2
0.0
150

300

450

600

Frequency (cm-1)

0

1000

2000

3000

Time delay (fs)Figure 6.2: Harmonic yield vs. pump-probe delay using (A) parallel (k) and (B) perpendicular (⊥) pump and probe polarizations. Harmonic yield is normalized to theharmonic emission at the negative pump-probe delay. Time-dependent 21st harmonic
yield for (C) parallel and (D) perpendicular polarizations. The insets in (C) and (D)show the Fourier transform, dominated by the N-N stretch mode at 255cm−1 . Figure
adapted from [90].

102of the ionization potential or rate due to the vibrational motion) cannot account for theobserved large modulation in HHG yield. Another possibility for the suppression of HHG
at the inner turning point is a contribution from a different electronic continuum, onethat has smaller recombination amplitudes for HHG. In Fig. 6.7 we plot the measured
intensity dependence of the HHG peak-to-peak modulation depth for different harmonicorders. The modulation depth increases with increasing laser intensity and decreases
with increasing harmonic order.
Fig. 6.3 plots the measured time-dependent ion yield after strong field ionizationof vibrationally-excited N2 O4 . For these data, the gas backing pressure was reduced to
100 torr to avoid strong space charge effects. The N2 O4 + and NO2 + ion yields do notexhibit any obvious oscillation structure and are therefore not plotted. Only the yieldof O+ was observed to be modulated by the vibrational excitation.
The spike near time zero is due to a coherent field effect. Moreover, the modulation depth of the O+ yield is <2%, which is much less than the 20 to 30% HHG
yield modulation. The observed small modulation in all ion yields agrees well with thecalculated results of the ionization structure factors, if both the Ag and B2g ionization
continua are contributing to the ion yield. In particular, since the N2 O4 + ionization
yield is approximately the same at the inner and outer turning points, ionization alone(i.e. modulation of the ionization potential or rate due to the vibrational motion) cannot account for the observed large modulation in HHG yield. Moreover, our findings
show that at the inner turning point, the molecule is ionizing but harmonic emission issuppressed. These data can be explained by a contribution from a state that is mostly
dark for HHG emission at the inner turning point.

103

Figure 6.3: Time-dependent O+ yield from N2 O4 after strong field ionization. The
modulation depth of the O+ yield is <2%, which is much less than the 20-30% modulationin the HHG yield. Figure adapted from [90].

104

6.4

Ruling out NO2 participation by interferometric measurementof the phase change in HHG from vibrating N2 O4
Because a small portion of NO2 (<20%) co-exists with N2 O4 in our sample, we had

to eliminate the possibility that heterodyne mixing of harmonic emission from N2 O4 andNO2 contributed to the observed modulation, . If the phase of harmonics emitted fromN2 O4 at the inner turning and outer turning points were different, interference between
emissions from NO2 and N2 O4 could contribute to the modulation observed. Such phasevariations could arise from intrinsic phase changes due to the differing ionization potentials at the inner and outer turning points of the vibration, or from different generating
ion states, i.e. Ag and B2g . Only the latter is consistent with our proposed mechanism. Using an interferometry technique demonstrated recently [55], we monitored thefringe pattern generated by interfering HHG from vibrationally excited and unexcited
N2 O4 molecules. No phase change in HHG emission was observed during the vibration,
within the sensitivity limit of our measurements. This null result is a clear indicationthat heterodyne mixing does not contribute significantly to our signal.
If the phase of the harmonic emission from N2 O4 at the inner turning and outerturning points of the vibration were different, interference between emissions from NO2
and N2 O4 could contribute to the observed HHG modulation, since a small fraction (<20%) of NO2 will be present in the gas. Such phase variations could arise from intrinsic
phase changes due to the differing ionization potentials at the inner and outer turning
points of the vibration, or from different generating ion states, i.e. Ag and B2g . To
rule out this possibility, we implemented a double foci interferometry measurement [55]
to monitor the fringe pattern (i.e. phase difference) between HHG from vibrationallyexcited and unexcited N2 O4 molecules. The result is plotted in Fig. 6.4. No phasechange in HHG emission from N2 O4 was observed during the vibration (Fig. 6.4(A)),
within the sensitivity limit of our measurements. This null result is a clear indication

105
that heterodyne mixing between NO2 and N2 O4 does not contribute to our modulated
HHG signal. In contrast, when we implemented the same interferometry technique tocompare the phase of HHG from rotationally aligned and unaligned CO2 molecules
during a rotational revival, a clear fringe shift corresponding to a π phase shift can beobserved for harmonic order 31 (Fig. 6.4 (B)).

6.5

Theoretical calculation
Our collaborators at National Research Council of Canada carried our the follow-

ing calculations for us. For this calculation, the electronic structure was calculated usinga modified aug-cc-pVTZ basis set, with f-type basis set functions deleted. Structuralparameters for the neutral N2 O4 ground state and the cation ground and electronically
excited states were optimized within the D2h point group at the complete active set
self-consistent field (CASSCF) level, with 16 molecular orbitals included in the active
space. This active space includes 13 occupied and 3 virtual orbitals. The overall composition of the active space was ag 3 au 1 b1g 1 b1u 3 b2g 2 b2u 2 b3g 2 b3u 2 . At this level,
structure of N2 O4 is in a good agreement with experimental results: rN −N =1.81Å (expt:1.78), rN −O =1.17 Å (expt: 1.19), αON O =134◦ (expt: 135). The effects of dynamicalcorrelations were treated with single-point second-order multi-reference perturbation
treatment (MCQDPT2), as implemented in GAMESS-US. Using the above parameters,
potential energy curves were calculated assuming adiabatic relaxation of all structuralparameters in neutral N2 O4 , other than the N-N bond length. For the N2 O4 cation
states, we used the instantaneous nuclear configuration of the optimized N2 O4 neutral
as a function of N-N bond length. The rationale for this is that during ∼1 fs time scale
electron rescattering process of HHG, the molecular structure does not have time torelax.
Vibrational wavefunctions were obtained by numerical solution of 1D effective-

106

Figure 6.4: Interference pattern obtained by combining HHG emission (15th order)
from vibrationally excited and unexcited N2 O4 . No obvious phase shift was observed
between the HHG at the inner and outer turning points. The top panel plots thetime-dependent HHG yield modulation by vibrations in N2 O4 . (B) For comparison,interference pattern obtained by combining HHG emission (31st order) from rotationallyaligned and unaligned CO2 , during a rotational revival. Near 0fs (CO2 aligned) the HHG◦
phase is shifted 180 relative to that of HHG at -250fs and 250fs (CO2 anti-aligned).
The top panel plots the time-dependent HHG yield modulation by a rotational revival
in CO2 . Time zero is at the center of the third quarter revival. Figure adapted from
[90].

107
diatom vibrational Hamiltonian, discretized on a 1.2Å<r<5Å grid. The effective massof the system was scaled by a factor of 0.7 to match the experimental fundamental
vibrational frequency in the neutral molecule. The structural factors were calculatedas:f (r) =

X
d

2

X
s

a (ǫd − ǫs ) hϕd |ϕs i hϕs |ψ (r)iwhere ϕs (ϕd )and ǫs (ǫd ) are vibrational wave functions and energies of the neutral(cation), and ø(r) is the initial vibrational wave packet (0.3Å FWHM Gaussian centeredat r). All bound vibrational states of the neutral are included in the summation. For
the cationic surface, the summation is over all states, both bound and continuum. Theenergy-dependent part of the ionization amplitude was taken as (atomic units)√a (ε) = ε1.5/ 2ε−0.25 exp − (2ε)1.5 /(3E) ,with E being the characteristic strength of the ionizing electric field (E ∼0.05 a.u.).
Approximation of the initial wave packet by a Gaussian ignores the anharmonicity of
the N2 O4 vibration and will not account for the real time evolution of the vibration wave
packets. But it is reasonable as a model of the R-dependent Franck-Condon factors forour experiment.
For N2 O4 molecules, ISRS in the strongly anharmonic ground state potential
results in large vibrational amplitudes, up to 0.6 Å (i.e. from ∼1.6 to 2.2 Å). To
understand the effect of this large excursion on the HHG process, we performed ab initio
calculations of the structure of both the N2 O4 neutral and cation states. The calculated
potential energy curves for the ground state of neutral N2 O4 , the ground state of thecation N2 O4 + (Ag ) and the first excited state of the cation (B2g ) are shown in Fig. 6.5(A). The equilibrium bond length of the Ag cation has a substantially elongated N-Nbond (2.21Å vertical, elongating to 2.25Å upon complete optimization). This bondlengthening is a consequence of HOMO ionization to the cation ground electronic state
removing a bonding electron. In contrast, ionization of the (HOMO-1) to the B2g excited108
state of the cation leaves the N-N bond relatively unchanged (1.75Å vertical, increasing
to 1.80Å upon relaxation). This picture is confirmed by the previously reported He(I)photoelectron spectra of N2 O4 which show a delayed onset and long progression to the
cation ground electronic state, compared with sharp lines and very limited progression
to the cation first excited state [100].
The significant difference in bond length for the ground and excited states of
the cation implies a strong bond-length dependence of the structural (Franck-Condon)
factors for tunnel ionization: the Ag ground state is expected to be favored at longer N-N
distances, whereas the B2g excited channel benefits when the N-N bond is compressed.
To quantify this argument, we performed a model calculation of the energy-dependent
contribution to the structural ionization factors using the potential energy surfaces
shown in Fig. 6.5 (A). (see also supporting text) The results (Fig. 6.5 (B)) show thatfor N-N bond lengths below 1.7Å, structural factors favor ionization to the B2g excitedstate. At longer bond lengths, ionization to the Ag ground state of the cation is favored,with the corresponding structural factor increasing up to RN −N =2.3Å. Thus, due tothe contribution of two ionization channels, the ion yield of N2 O4 + is not expected tochange significantly during the vibration, consistent with experiment.

6.6

Saturation due to the depletion of ground state
At the relatively high laser intensity used here, saturation due to the depletionof the neutral N2 O4 population may become an important factor. In this regime, thetotal number of emitters of each type is determined by the ratio of the ionization rates
for each species, rather than by the individual rates. The calculated ratio of the Ag /B2g
structural factors in N2 O4 increases monotonically with RN −N , with the B2g state as
the preferred channel at short bond lengths, whereas the Ag state dominates when thebond is elongated. Thus, the relative importance of the two channels remains the same,

109

14
-6

8.0x10+

Structural ionization factor (arb. units)

N2O4 cation, B2g state

13

Energy (eV)

12

11
+

N2O4 cation, Ag state

3

2

1

N2O4 ground state

0
1.0

1.5

2.0

2.5

3.0

3.5

4.0

-6

7.0x10

Ionization to Ag-6

6.0x10-6

5.0x10-6

4.0x10

Ionization to B2g-63.0x10-6

2.0x10

1.6

1.8

2.0

2.2

Bond length (Angstroms)

Bond length (Angstroms)

(A)

(B)

2.4

2.6

Figure 6.5: (A) Calculated MCQDPT2//CASSCF potential energy curves for neutral
N2 O4 (bottom) and the first two cation states (top). (B) Structural factors for ionization
calculated at different bond lengths. At the short bond length, ionization favors the firstexcited state of the ion (B2g continuum) whereas the ground Ag continuum dominate
at long bond lengths. Figure adapted from [90].

110

1.6

1.2

H25 ||

2

2

Recombination dipole: |d| (Bohr )H19 ||
1.4

B2g

Ag

1.0

H29 ||
0.8

H19 -⊥

0.6

H25 -⊥

0.4

H29 -⊥

0.2
0.0
1.4

1.6

1.8

2.0

2.2

2.4

2.6

Bond length (Angstroms)

(A)

(B)

Figure 6.6: (A) Dyson orbitals corresponding to ionizing to the Ag cation state andthe B2g cation state. The calculated equilibrium bond lengths for the neutral, Ag andB2g cation states are 1.808 Å (exp. 1.756Å), 2.248 Å and 1.8 Å, respectively. (B)Recombination dipoles of harmonics at different bond lengths for parallel (red, k) andperpendicular (blue, ⊥) pump-probe polarization. Figure adapted from [90].

111even in the presence of saturation. The observed increase in modulation depth withincreasing laser intensity (Fig. 6.7), is in good agreement with this two-continuum-statesmodel. If the HHG process involved emission only from a single continuum transition, adecreasing modulation depth with increasing laser intensity should be observed because
ionization saturation at the outer turning, which is reached at the lower laser intensity
due to lower ionization potential, will lead to reduced modulation depth.

6.7

Origins of HHG suppression at the inner turning point
To calculate the recombination dipoles, the amplitude of the ionization or recom-

bination process within a given ionization channel is determined by the 1-particle dipole
matrix element between the Dyson orbital and the continuum wave function at a given
energy. We treat the continuum wavefunctions in the strong-field eikonal-Volkov approximation [40], with the molecular potential included in the Hartree approximation.
The residual non-orthogonal contributions in the continuum wavefunction are treatedwith the exchange corrections of ref. [39]. The recombination dipoles are coherently
averaged over relative orientations of the molecular frame and the probe pulse. The
angular distribution of the N-N bond in vibrationally excited N2 O4 molecules createdby pump pulse was assumed to be cos2 θ. The final results are only weakly sensitive tothe detailed shape of the distribution.
For the propagation of the liberated electron in the continuum, the long-range partof the molecular potential is not significantly influenced by intramolecular vibrations,and no additional modulation of the HHG signal is expected. Therefore, we now consider
the electron recombination step. To this end, we calculated the overlap between the
N-electron wave function of the neutral species, and the (N-1)-electron wave functionof the ion – the Dyson orbital. This calculation captures the change in the electronic
structure of the molecule upon electron removal or recombination. Dyson orbitals for

112

0.24
0.22

H17
H15
H21
H19

0.20

Modulation Depth

0.18
0.16
0.14

H23
0.12
0.10
0.08
0.06
0.04

H25

0.02

H27

0.00

1.2

1.4

1.6
14

1.8

2

Laser Intensity 10 W/cm

Figure 6.7: Laser intensity dependence of the vibrational modulation depth for different harmonics, showing an increasing modulation depth with increasing laser intensity.
Figure adapted from [90].

113
the two significant ionization channels, calculated at the equilibrium geometry of theneutral species, are shown in Fig. 6.6(A). The final recombination dipoles for the
Ag channel as a function of both their N-N bond separations and harmonic order are
shown in Figure 6.6(B). As a result of the presence of nodal planes along all principal
directions, the excited ion state channel (B2g ) is suppressed. Nodal planes both decrease
recombination matrix elements and reduce recollision probability.
The radial dependence of the calculated recombination dipoles d is sensitive tothe harmonic order. At low harmonic orders (H17 to H21), the matrix elements for theparallel pump/probe orientation increase with the N-N bond length, leading to a doubling in harmonic radiation intensity at RN −N =2.1Å (|dH19 |2 ≈ 1.6 Bohr2 ) comparedto RN −N =1.5Å (|dH19 |2 ≈ 0.84 Bohr2 ). At higher orders (H27, H29), the variation of|d|2 with the bond length does not exceed 15%.
This behavior is consistent with the observed decrease in the modulation of harmonic intensity for higher harmonic orders (Fig. 6.2 (A)). The lower modulation depth
observed for perpendicular polarization of the pump and probe pulse is also consistent with the overall 0.37 times≈ decrease of the recombination matrix elements forthis geometry. For both geometries, the modulation remains in phase for all harmonics, indicating that the observed dependences cannot be explained by the structuraldependence of the recombination matrix elements.
Even though the cation excited state (here B2g ) does not contribute significantly
to HHG emission in N2 O+
4 , in other molecules emission from different ionization continua
will add coherently; thus observables such as the ellipticity and phase shift of the HHG
emission emerge as a sensitive diagnostic of dynamics in polyatomic molecules.

114

6.8

OutlookThis discovery brings both challenges and opportunities to the application ofstrong field ionization and HHG to molecular structure and dynamics studies. Whereasa simple picture involving only a single HOMO orbital may be sufficient for simple diatomic molecules, generalization to larger molecules undergoing large structural changes
will require more complicated theoretical treatments. On the other hand, the sensitivity of strong field ionization and HHG to different ionization continua promises thattechniques that monitor tunneling ionization, photoelectron distributions and HHG simultaneously can uncover detailed information on electronic and nuclear structure anddynamics in polyatomic molecules.

Chapter 7

Summary and Future directions

7.1

Advantages and disadvantages of HHG spectroscopy
In summary, we have demonstrated that high harmonic generation —a strong

field phenomenon initiated by ionization and completed by the electric field driven
recollision— can be a very powerful tool for probing molecular structure (Chapters
3, 4, and 5) and monitoring dynamics (Chapter 6). HHG emission from aligned anddynamically excited molecules carries information of molecular structure and dynamics,
such as phase and amplitude information on the molecular orbital and adiabatic coupling
between electronic and nuclear motion in molecules. As a microscopic collision process,the colliding electron current in HHG is actually quite high as compared to conventional
electron colliders [99]. Furthermore, the recollision process in HHG is also a coherent
process, which means that it can be considered as an interference between the continuum
and bound part of the electron wave function. Forthermore, the state selectivity oftunnel ionization and the time resolution of the HHG spectroscopy technique make ita useful molecular spectroscopy method, that is complementary to weak field methods
such as photoelectron spectroscopy.
Notwithstanding these advantanges, HHG spectroscopy also presents important
disadvantages as compared to weak field probing methods. The first is the presence ofthe strong laser electric field during the entire process. The molecular ion with which theelectron collides is under distortion by the strong laser field, rather than under a field-

116
free condition. The second disadvantage is the Coulomb laser coupling during the entire
process. The recolliding electron wave packet originates from the molecular HOMO andis influenced by the Coulomb potential when it is accelerated in the continuum. This
makes it a less that perfectly well-controlled probe.
However, since HHG in molecules offers more information than HHG from atoms,
the bright future of the molecular HHG spectroscopy lies in the understanding of thestrong field process itself. Our data and work clearly show that the understanding ofatoms and molecules in a strong laser field, especially HHG from molecules, is far fromcomplete. Ultimately, a theory which can combine the predictive power of the TDSE
with the physical insight of the three-step model is still needed.

7.2

Future directions
The techniques developed in this work can be potentially extended to other ques-

tions and systems of strong field physics and chemistry. We list a few examples here.
(1) HHG using driving laser wavelengths longer than 790 nm (in the mid-infrared
range) has recently attracted considerable attention. The advantage of usingof a long wavelength driver is that it can extend the cutoff of the generated
harmonics, because Up is ∝ λ2 . A long wavelength driver also reduces the levelof ionization, which opens the door for HHG experiments on many chemicallyinteresting molecules with a low Ip . For these molecules, only very low-orderharmonics can be generated by a 790 nm laser. However, HHG conversion efficiency decreases quickly with the increasing driving laser wave length, because
the electron wave packet spreads more when it travels in the continuum, reducing the recollision probability. This decreasing efficiency might reduce the HHG
flux to the point where the a sufficient signal-to-noise ratio can not be achieved.
(2) For molecules with a permanent dipole moment, such as N2 O, it is possible

117
to orient the molecules by either a static electric field or a strong half-cycle
pulse at THz frequency. Even-order harmonics can be generated from oriented
molecules.
(3) It will be interesting to study more complex molecules such as long carbon chain
molecules, which are in liquid form at room temperature. Our current setup islimited to gas phase molecules. In principle, we can inject high-density vapor
into the chamber by raising the temperature of the jet.
(4) The recent proposed relationship between the recollision step of HHG and photoionization seems to be a very clear model. Since the HHG yield is related
to the differential photoionization cross-section, it would be interesting to investigate the relationship of the HHG polarization state and the photoelectron
angular distribution in photoionization.
(5) For the electronically-excited molecular states, a careful measurement of thepolarization state of the HHG emitted may reveal interesting physics. From
states with different symmetry, it may be possible to generate HHG with perpendicular polarizations.

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Appendix A

Positive Dispersion Cavity Dump Ti: Sapphire Oscillator

In this appendix, we present the first demonstration that up to 0.45 µJ pulses
can be obtained from a cavity-dumped Ti: sapphire oscillator stably operating in thepositive dispersion regime [101]. The output pulse can be compressed to 60 fs and used
to generate a white light continuum through self-filamentation in a thin sapphire plate.

A.1

Introduction
Cavity dumping is a standard technique for generating moderate-energy pulses

from femtosecond Ti: sapphire laser oscillators [102, 103, 104, 105]. A cavity dumper
can increase the effective output coupling from a Ti: sapphire oscillator from 5-10% up
to ∼80%, giving an order of magnitude increase in pulse energy from the laser, at theexpense of reduced repetition-rate. Pulse energies of >200 nJ have been reported fromelectro-optically cavity dumped Ti:sapphire oscillators [104], but at very low repetitions
rates (kHz) and with limited repeatability. More generally, multi-pulse and continuous wave (CW) breakthrough instabilities from excessive Kerr nonlinearity have limited
the obtainable stable-and-repeatable energy to tens of nJ energy and ∼ 100mW average power. Other materials such as Yb:glass [106] and Yb:KYW [107], have operated
mode locked and cavity dumped by employing semiconductor saturable-absorber mirrors (SESAMs). Although µJ pulse energies can be generated by these lasers, the peak
power is only a few MW since the pulse duration is limited to a few hundred fs. For

128applications in materials micromachining [108], nonlinear frequency conversion [109],and femtosecond white-light continuum generation [110], a MHz repetition-rate sourcewith ∼µJ pulse energy and sub-100 fs pulse duration would be desirable.
An alternative to cavity dumping is to extend the length of the laser cavity to
reduce the repetition rate and increase the per-pulse energy [111, 112, 108, 113]. The
extreme example of this is to include a Herriott-type multi-pass telescope in the standard oscillator cavity to obtain repetition rates as low as 2 MHz [114], corresponding to
a 150m cavity length. To avoid excessive Kerr nonlinearity due to the high intracavity
peak power, these oscillators are operated either with large negative or small positive
intracavity dispersion, and in some cases with SESAMs to support stable mode locking[112, 114, 115]. 43 fs, 150nJ pulses have been generated by working in the large negative
dispersion regime (NDR) [112] . In the positive dispersion regime (PDR) [116] , thepulse in the cavity is broadened by the combined action of positive group velocity dispersion (GVD) and self phase modulation (SPM), and the laser is mode locked by the
dynamic gain saturation, spectral filtering , and self amplitude modulation (SAM) or
Kerr-lens mode-locking (KLM) [115]. In PDR, a heavily chirped ps pulse is generated
that can be externally compressed to <100 fs [113, 114]. The long pulse duration inside
the laser in the PDR offers much better energy scalability, with acceptable pulse quality.
Recently 130nJ pulse at 11MHZ and 505nJ pulse at 2MHz has been obtained from thesechirped-pulse multi-pass cavity (CPMC) oscillators, with peak power as high as 10MW
and 1∼2W average power using a 10W pump laser [114].
Here, we show for the first time that it is possible to combine cavity dumping with thepositive dispersion regime of operation. Using a configuration similar to the standard(prism dispersion controlled) cavity-dumped geometry [105], sub-100fs pulses with peak
power as high as 7.5MW at a variable repetition rate as high as 2 MHz can be generated stably and reliably. Compared with the CPMC oscillator, this positive dispersion
cavity dumped (PDCD) oscillator is substantially more energy-efficient, producing up

129
to 450nJ pulse using as low as 6.5 W pump power. Furthermore, it has an easily variable repetition-rate and occupies a footprint of only 0.3m2 —no larger than a standard
Ti: sapphire oscillator. This oscillator fills a gap between standard Ti:sapphire oscillators and more-complex oscillator-amplifier systems [30]. Finally, we demonstrate stablefilament-induced white light generation from 400nm to 1µm using this laser.

A.2

Laser setup and performance
The laser system setup and external double-pass prism pair compressor is shown in

Fig. A.1. A Bragg cell driver and 18W amplifier (CAMAC) drive a fused silica cavity
dumper (Harris). The laser repetition-rate is detected by a photodiode, conditioned
using a constant fraction discriminator (CFD, Phillips Scientific) and slightly amplified
by a pulse generator (Hewlett-Packard 8082A), before going into the Bragg cell driver.
All the mirrors are standard dielectric mirrors with low dispersion. The path length in
the Ti: sapphire crystal is ∼5 mm.
With a 5.3% output coupler, the laser can be mode locked stably in both the NDR
and PDR. In the NDR, the pump power is limited to below 5W to avoid instabilities. For
the transition from negative to positive dispersion, we simply add material dispersion
by translating the first intracavity prism. Near the zero dispersion point, the lasershows self Q-switched mode-locking behavior, but with more positive dispersion it settles
into a stable, hard-edge, spectrum characteristic of a standard Ti:sapphire oscillator
operating in the PDR [116] . Increasing the pump power to the full 10.4W once in the
PDR, we then optimize the intracavity dispersion and the KLM parameters, i.e. therelative position of the Ti: sapphire crystal and the focusing mirrors. In translating theprism from the negative dispersion point, we estimate that stable operation with ∼40
nm bandwidth is obtained with a net intracavity dispersion of less than 40fs2 . Thisvalue is significantly smaller than previous reported using SF10 prisms for dispersion

130

Figure A.1: The setup of the positive dispersion cavity dump oscillator.

131
compensation in a regular oscillator [116], or using fused silica prisms in multi-passcavity [114]. The CW output from the output coupler is 2W when pumped by 10.4 W
in the PDR, indicating an intracavity pulse energy of 500nJ. The crystal was cooled to -3◦ C using antifreeze coolant, and we saw no evidence of thermal lens induced degradationof slope efficiency even at full pump power. Given the very high intracavity pulse energy,
non-resonant re-absorption of the 780 nm circulating light might be an issue; however,this absorption appears to be minimal.
A further increase in the intracavity power can be obtained by replacing the output coupler with a standard broadband high reflector (Newport UF20). Stable mode
locking operation is sensitive to the relationship between cavity adjustment and dispersion. By comparing the integration of the detected intracavity spectrum with theoutput coupler used, we estimate that up to 60W intra-cavity power and 750nJ per pulse
energy can be obtained at pump power as low as 6.5 W. Stable mode locking, however,is not obtained for higher pulse energies. We believe the limitation is set by saturationof the Kerr lens induced differential gain in the Ti: sapphire crystal, which can occur
when the spot size of the red light becomes smaller than the pump light spot size. Robust operation at near-optimum power can be obtained with a high-reflector and 6.5 W
pump power. We have used both a Spectra-Physics Millennia X and Coherent Verdi 6
pump laser with comparable results.
When the intracavity peak-power is increased by substituting the output coupler
with a high reflector, the spectrum is further broadened, as shown in Fig. A.2 (blue).
In this regime, we could obtain up to 60% dumping efficiency without encountering
instabilities such as period-doubling or self Q-switching. In the NDR, cavity-dumping
only slightly shifts the laser spectrum. However, in the PDR, the spectrum width andshape can be modified dramatically at MHz dumping frequencies, as shown in Fig. A.2(red). This results from the fact that when the output coupler is replaced with a highreflector, the overall cavity loss (and therefore the intracavity pulse energy) is dominated

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PDR with HR and Dumping off
PDR with HR and 0.8MHz Dumping

Intensity (A.U.)

4000

3000

2000

1000

750

760

770

780

790

800

810

Wavelength (nm)Figure A.2: Spectrum from the cavity-dumped laser in the positive dispersion regime
with 6.5 W pump, with the dumper on and off.

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by the cavity dumping. Furthermore, in the PDR, the Kerr lens is expected to play amore important role in determining the spectrum inside the cavity than it would for the
standard NDR solitary mode of operation.
To obtain the highest pulse energy in a stable mode of operation, we used an RF
spectrum analyzer (Agilent E4410B) to monitor the pulse train, and limited the Bragg
driver power to below where additional amplitude noise is induced by cavity dumping.
A typical microwave spectrum of the intracavity modulated pulse train is shown in Fig.
A.3.

20

RBW: 3KHz

Spectraum (dB)

0

-20

-40

-60

-80
76

77

78

79

80

81

82

Frequency (MHz)Figure A.3: Typical microwave spectrum of the intra-cavity modulated pulse train.

The dependence of the cavity dumped pulse energy on dumping frequency isshown in Fig. A.4. The peak pulse energy is obtained at 0.8MHz; lower dumping rates
give slightly lower energy than at 0.8 MHz, while higher dumping rates give proportionately lower pulse energy. The peak at 0.8 MHz results from relaxation oscillations thatgive an energy overshoot at about 1.25 µs after dumping of the previous pulse.

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Using a fast photodiode (100 ps resolution), combined with a long scan-range(>100 ps) autocorrelator, and a high resolution spectrometer, we confirmed that nosecondary pulses are generated even at the highest intracavity peak power. We alsomeasured the intensity contrast ratio between the dumped output pulse and the neighboring pulse. The delay of the Bragg cell driver can be adjusted to give a <1:100 ratio
for both the pre- and the post-pulse.
The uncompressed pulse emitted from the laser has duration of about 1.2ps. Usinga simple compressor consisting of two equilateral SF11 prisms with 90cm separation, we
recompressed the pulse with high (>90%) throughput. Double-passing the compressor
gives approximately –10000 fs2 GVD and -50000fs3 third-order dispersion. A frequencyresolved optical gating (FROG) measurement of the recompressed pulse is shown in
Fig. A.5. The FWHM pulse duration is 60fs, is ∼1.3x transform limited, with apeak power of ∼7.5MW. The satellite ripples are generated by the sharp edge of thespectrum and the residual third-order dispersion of the prism compressor. The PDCD
oscillator and CPMC oscillator have similar sharp edge spectra and satellite pulses
in their temporal profiles [113, 114]. We observe slightly longer pulse duration (60fs)
than in the case of the CPMC oscillator (45fs at 2MHz repetition rate), because ourcompressor can not compress the pulse to the transform limit of the spectrum (∼46 fs).
Careful engineering of the intracavity dispersion can further broaden the spectrum. The
use of a high-throughput pulse shaper or specially-designed TOD compensating chirp
mirrors should result in nearly transform-limited pulse duration. As is generally foundin lasers operating in the PDR [114, 116], the spectral width and chirp of the output
pulse strongly depends on the intracavity dispersion, pulse energy and cavity alignment.
Thus the extra cavity dispersion must be re-optimized when the operating parametersof the laser change.
To demonstrate the unique utility of this laser, we generated a white light continuum by focusing the compressed 0.8MHz repetition-rate pulse into thin sapphire and

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500

0.0

0.5

1.0

1.5

PulseEnergy
Power

2.0
700

500

400

400
300
300

200
100

Average Power (mW)

Pulse Energy (nJ)

600

0
200
-0.25 0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 2.25

Dumping Frequency (MHz)Figure A.4: Pulse energy, and average power as a function of dumping rate in the PDR,
with 6.5 W pump power.

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1.0

Phase
Intensity

3

2
0.6

0.4
1

Phase (rad)Normalized Intensity

0.8

0.2

0.0

0
750

760

770

780

790

800

810

Wavelength (nm)(a)
1.0Nomalized Intensity

0.8

FWHM 60fs

0.6

0.4

0.2

0.0
-400

-300

-200

-100

0

100

200

300

Time (fs)(b)

Figure A.5: Spectral (a) and time domain (b) profile of prism-recompressed pulse,
reconstructed from FROG measurement.

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fused silica plates using a 6 cm FL aspheric lens. Filament-induced white light generation could be observed without the need for careful optimization. The use of sapphire
avoids rapid damage and allows extended operation of the white light source. The
white light spectrum measured using an optical spectrum analyzer (Ando AQ-6315E)
is shown in Fig. A.6. The inset of Fig. A.6 is a digital camera image of the continuum.
Although the center of the white light profile is stable, we observe a long time-scale,periodic (∼10 seconds) instability in the red ring. We speculate that this results froma thermal cycling due to the relatively high repetition-rate and average power of thisfilament compared with past work. To our knowledge these are the first data presented
on white-light continuum from a filament generated by the unamplified output directlyfrom a sub-100 fs Ti: sapphire laser oscillator. One recent paper using multi-pass cavity
oscillators operating in the PDR with much higher pump laser power, has also mentioned white light generation [117]. Past work using a cavity-dumped Yb:KYW laser
with an additional stage of spectrum broadening and re-compression before generating
filamentation [107, 109], greatly complicated the setup compared with the one discussed
herein.

A.3

Conclusion
In conclusion, we have demonstrated the first cavity-dumped Ti: sapphire oscil-

lator working in the positive dispersion regime. This results in a dramatic enhancementin the average and peak output power from such a laser, while still maintaining pulse
duration of well under 100 fs. We believe that this pulse energy is currently limited
by saturation of the KLM, and optimum operation can be obtained using a relativelymodest 6 Watt pump laser. Further improvement in the pulse energy might be obtainable using a SESAM, either through an increase in intracavity pulse energy, through anincreased dumping of the intracavity pulse before instabilities arise, or through more

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Figure A.6: Spectrum of the filament-induced white light. Inset: A digital photographof the generated white light continuum.

139
freedom to optimize the power without losing mode locking. It is likely that energies
exceeding 1 µJ can be obtained, and possibly much more with aggressive cooling of
the crystal [118]. Such a compact and reliable high peak-power laser could be used
for a variety of scientific and industrial applications such as micromachining, nonlinear
frequency conversion, broad-band fs spectroscopy, and even strong field physics experiments. Carrier-envelope stabilization of such a laser oscillator, or using it as a seed
source for CW-pumped active amplification [118, 119] to the tens of µJ level at MHz
repetition rate may also be possible.