Generation, Temporal Characterization andApplications of Femtosecond-/ Attosecond
Extreme Ultraviolet Pulses
byIsabell Thomann
Diplom Physik, ETH Zürich, 2001

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:
Generation, Temporal Characterization and Applications of Femtosecond-/
Attosecond Extreme Ultraviolet Pulses
written by Isabell Thomannhas been approved for the Department of Physics

Margaret M. Murnane

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
Thomann, Isabell (Ph.D., Physics)
Generation, Temporal Characterization and Applications of Femtosecond-/ Attosecond
Extreme Ultraviolet Pulses
Thesis directed by Prof. Margaret M. Murnane

The work of this thesis is arranged into three parts:(A) Generation and temporal characterization of extreme ultraviolet(EUV) attosecond pulses. In this work I present the generation and first temporal characterization of sub-optical cycle EUV radiation generated in a noble-gas filled
hollow-core waveguide. Two regimes of EUV radiation were characterized, ranging from
200 attoseconds to ∼ 1 femtosecond in duration. The first regime that was characterized distinguishes itself from EUV radiation generated by other methods by its narrow(∼ 1 eV) spectral width, its simple energy tunability and its temporal confinement to∼ 1 femtosecond. In the second regime, single isolated pulses of 200 attoseconds duration (and accordingly larger bandwidth) were generated. In both regimes dynamic
phase-matching effects create an extremely short time window within which efficientnonlinear conversion is possible, while it is suppressed outside this window. Temporalcharacterization of the generated EUV pulses was approached by two-color pump-probe
photoelectron spectroscopy. Therefore an efficient photoelectron spectrometer was set
up, detecting electrons in a 2π collection angle. For the interpretation of the experimental data, an analytical model as well as an iterative algorithm were developed, toallow extraction of complex EUV waveforms. The demonstrated radiation will allow
for time-resolved studies of the fastest processes in molecules and condensed matter,
while at the same time ensuring adequate energy resolution for addressing individual
electronic states.
(B) Application of a COLTRIMS reaction microscope in combination

iv
with femtosecond EUV pulses to questions in molecular physics. The combination of the sensitive detection capabilities of a COLTRIMS reaction microscope with thehigh time resolution of pump-probe experiments using femtosecond extreme-ultraviolet
pulses makes it possible to answer very fundamental open questions in molecular physics
such as the dependence of molecular photoionization on the molecular orientation. To
this end, molecules were impulsively aligned by means of femtosecond pump pulses.
The excited molecular rotational wavepacket experiences revivals that continue longafter the pump pulse has left. During such revivals, the molecular axes change theirorientation from parallel to perpendicular with respect to the polarization of the pumppulse within a few hundred femtoseconds. Therefore photoionization by femtosecond
EUV pulses with variable delay during a revival is equivalent to photoionization ofmolecules with varying orientation. With this novel method the orientational dependence of single-photon photoionization of N2 and CO2 into non-dissociating channels,
as well as for a long-lived state of CO2+ was measured for the first time.
(C) Carrier-envelope-phase (CEP) stabilization of a femtosecond chirped
pulse amplifier. Lastly, CEP stabilization of intense laser pulses from a chirped pulse
amplifier was realized. For amplifier systems containing a pulse stretcher and compressor based on diffraction gratings, an increased susceptibility to CEP fluctuations
had been expected prior to this work. Therefore the pulse stretcher and compressor
system were examined separately in a first step, and the introduced CEP fluctuations
were found to be insignificant. The CEP stability of the full amplifier system was thencharacterized, and excellent long-term stability was shown. With this work a scaling of
the energy of CEP-stabilized pulses into the joule range becomes possible. In contrast
to absolute frequency measurements with low-energy femtosecond pulses which requirestability in the frequency range, the interest in stabilized high-energy pulses is to control the entire electric field of intense laser pulses in the time domain with attosecond
precision, to allow full control of the dynamics of electrons in intense light fields.

Dedication

To my grandparents, parents and Volker.

vi

Acknowledgements

First of all I would like to thank my advisors Margaret Murnane and Henry
Kapteyn for always giving me the opportunity to pursue the research I was interestedin, for their generous advice, and for teaching me a lot about ultrafast physics. There
are a number of people who have directly contributed to the work in this thesis: In the
few months I worked with him, I have learned a lot from postdoc Wen Li. Thanks to
Emily Gregonis for various contributions to the EUV temporal characterization setup,
and to Robynne Lock for sharing her code and for doing calculations regarding thealignment of molecules. I thank Oren Cohen and Alon Bahabad for their collaboration,and for various supporting numerical calculations on EUV generation. Thanks also to
everybody else in the group past and present, for their assistance and for making thisPh.D. enjoyable.
During this thesis I had various fruitful collaborations outside the group: Thanks
to Jason Jones and Jun Ye, for giving me the opportunity to help explore novel phasestabilization techniques for ultrafast lasers. Thanks to Xuan Liu and Rick Trebino at
Georgia Tech for a fruitful collaboration on numerical codes for the temporal characterization of EUV radiation. I also thank Farhad Salmassi, Andy Aquila and Yanwei Liu
at Berkeley for fabricating the EUV mirrors used in my temporal characterization and
COLTRIMS experiments. Last but not least, many thanks go to the people at NIST,
where I spent a very interesting and rewarding time at the beginning of grad school:
Leo Hollberg, Scott Diddams, Kristan Corwin, Albrecht Bartels, Nate Newbury andvii
Brian Washburn.
This work would not have been possible without the excellent support of the JILA
electronics and machine shops, and the JILA computing staff and the JILA office staff:
All of them significantly ease the life of a grad student! In particular I thank Terry Brown
and James Fung-a-Fat for always being available for advice in the CEP stabilization
project. Invaluable advice and assistance also came from David Alchenberger, Thomas
Foote, Hans Green, J. R. Raith, Brian Lynch and Jeff Sauter. Thanks also to Dirk
Mueller, Sterling Backus, and Kendall Read from KMlabs for their assistance.
I also thank family and friends.

viii

Contents

Chapter
1 Introduction

1

1.1

Background: Relevant Time Scales . . . . . . . . . . . . . . . . . . . . .

2

1.2

Overview of work in this thesis . . . . . . . . . . . . . . . . . . . . . . .

3

1.3

A carrier-envelope phase (CEP) stabilized amplifier . . . . . . . . . . . .

4

1.3.1

CEP stabilization of low-power femtosecond pulses . . . . . . . .

6

1.3.2

CEP stabilization of amplified ultrafast laser pulses. . . . . . .

6

Generation of coherent ultrafast extreme-ultraviolet radiation . . . . . .

9

1.4.1

The three-step model . . . . . . . . . . . . . . . . . . . . . . . .

9

1.4.2

Advanced single-atom models for HHG. . . . . . . . . . . . . .

18

1.4.3

Macroscopic effects on HHG emission: Phase matching . . . . . .

18

1.4.4

Attosecond pulse generation in a hollow waveguide . . . . . . . .

21

1.5

Temporal Characterization of ultrafast EUV radiation . . . . . . . . . .

24

1.6

Applications of femtosecond / attosecond pulses . . . . . . . . . . . . . .

25

1.6.1

Molecular physics . . . . . . . . . . . . . . . . . . . . . . . . . . .

25

1.6.2

Condensed matter systems . . . . . . . . . . . . . . . . . . . . .

25

1.6.3

Strong-field physics . . . . . . . . . . . . . . . . . . . . . . . . . .

26

The COLTRIMS reaction microscope . . . . . . . . . . . . . . . . . . . .

28

1.4

1.7

1.7.1

Opportunities of fs-EUV pulses combined with COLTRIMS detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

28

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1.8

Organization of this thesis . . . . . . . . . . . . . . . . . . . . . . . . . .

2 A carrier-envelope phase (CEP) stabilized amplifier
2.1

29
30

Introduction, Motivation and Difficulties . . . . . . . . . . . . . . . . . .

30

2.1.1

Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

30

2.1.2

Where do CEP fluctuations come from? . . . . . . . . . . . . . .

31

2.1.3

History and methods of CEP stabilization . . . . . . . . . . . . .

33

2.1.4

CEP concerns with amplified pulses . . . . . . . . . . . . . . . .

35

2.2

A CEP stabilized oscillator . . . . . . . . . . . . . . . . . . . . . . . . .

36

2.3

Investigation of a grating-based stretcher/compressor for carrier-envelope

2.4

phase stabilized femtosecond pulses . . . . . . . . . . . . . . . . . . . . .

42

2.3.1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

43

2.3.2

Setup and measurement methods . . . . . . . . . . . . . . . . . .

45

2.3.3

Results and discussion . . . . . . . . . . . . . . . . . . . . . . . .

47

2.3.4

Conclusions regarding grating-based stretcher compressor systems

51

Long-term carrier-envelope phase stability from a grating-based, chirped
pulse amplifier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

51

2.4.1

Electronics for CEP stabilized amplifier . . . . . . . . . . . . . .

52

2.4.2

Measurements and results . . . . . . . . . . . . . . . . . . . . . .

53

3 Generation and temporal characterization of attosecond pulses

61

3.1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

62

3.2

Attosecond pulse generation methods . . . . . . . . . . . . . . . . . . . .

65

3.3

Attosecond pulse measurements . . . . . . . . . . . . . . . . . . . . . . .

67

3.3.1

EUV EUV autocorrelation. . . . . . . . . . . . . . . . . . . . .

69

3.3.2

Laser-assisted photoemission . . . . . . . . . . . . . . . . . . . .

69

3.3.3

Attosecond streak camera . . . . . . . . . . . . . . . . . . . . . .

73

3.3.4

RABBITT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

75

x
3.3.5

XUV SPIDER . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.3.6

Frequency-Resolved Optical Gating for Complete Reconstructionof Attosecond Bursts (FROG CRAB) . . . . . . . . . . . . . . .

3.4

75

76

Theoretical background: EUV photoionization in the presence of a NIR
driving laser field. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

76

3.5

Generalized projections (GP) algorithm for FROGCRAB . . . . . . . .

79

3.6

Modifications to the GP algorithm . . . . . . . . . . . . . . . . . . . . .

81

3.6.1

Atto- and harmonic chirp . . . . . . . . . . . . . . . . . . . . . .

85

Experimental setup and photoelectron detection geometry . . . . . . . .

87

3.7

3.7.1

Magnetic bottle time-of-flight spectrometer, electronics and dataacquisition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.8

Temporal characterization of attosecond waveforms in the sub-optical
cycle regime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.9

89

93

Characterizing isolated attosecond pulses from hollow-core waveguides
using multi-cycle driving pulses . . . . . . . . . . . . . . . . . . . . . . . 103
3.9.1

Direct simulations of FROG CRAB traces . . . . . . . . . . . . . 105

3.9.2

Interpretation of single attosecond pulse generation mechanism . 113

3.9.3

Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . 117

4 Combining femtosecond-EUV pulses with the COLTRIMS technique as a novel
spectroscopy method in molecular physics

120

4.1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

4.2

The COLTRIMS technique . . . . . . . . . . . . . . . . . . . . . . . . . 122

4.3

Components of a COLTRIMS apparatus . . . . . . . . . . . . . . . . . . 124
4.3.1

Supersonic gas jet and COLTRIMS chamber . . . . . . . . . . . 124

4.3.2

Electric and magnetic fields . . . . . . . . . . . . . . . . . . . . . 126

4.3.3

Electron and ion trajectories . . . . . . . . . . . . . . . . . . . . 129

xi

4.4

4.5

4.3.4

Detectors and electronics . . . . . . . . . . . . . . . . . . . . . . 132

4.3.5

Data analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135

4.3.6

Coincidence detection . . . . . . . . . . . . . . . . . . . . . . . . 135

4.3.7

COLTRIMS detection efficiency and optics efficiency . . . . . . . 136

Molecular alignment methods . . . . . . . . . . . . . . . . . . . . . . . . 136
4.4.1

Field free (nonadiabatic) molecular alignment . . . . . . . . . . . 138

4.4.2

Quantum mechanical description of rotational coherent wave packets140

4.4.3

Practical considerations for strong molecular alignment . . . . . 142

Measuring neutral-to-ionic transition dipoles: Angular Dependence of theSingle-Photon Ionization of Aligned N2 and CO2 . . . . . . . . . . . . . 143
4.5.1

Motivation for this experiment . . . . . . . . . . . . . . . . . . . 144

4.5.2

Past measurements on transition dipoles . . . . . . . . . . . . . . 145

4.5.3

Experimental setup and technique for measuring angle dependent
photoionization of molecules . . . . . . . . . . . . . . . . . . . . . 149

4.5.4

Experimental Results: Angular Dependence of the Strong-Field
Ionization of Aligned N2 and CO2 . . . . . . . . . . . . . . . . . 151

4.5.5

Experimental Results: Angular Dependence of the Single-Photon
Ionization of Aligned N2 and CO2 . . . . . . . . . . . . . . . . . 151

4.5.6

Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155

4.5.7

Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . 160

4.6

Towards molecular-frame photoelectron angular distributions . . . . . . 161

4.7

Other results obtained with COLTRIMS . . . . . . . . . . . . . . . . . . 166
4.7.1

Coulomb explosion following photoionization of N2 O at 43 eV . . 166

4.7.2

EUV photoionization of O2 at 43 eV . . . . . . . . . . . . . . . . 167

5 Outlook

170

xii
Bibliography

172

xiii

TablesTable
4.1

Typical potential settings for COLTRIMS electric field. . . . . . . . . . 135

4.2

Comparison of Anisotropy Parameters (β) between Experiment and Theory160

xivFiguresFigure1.1Time scales of matter and light relevant to this thesis. . . . . . . . . . .

1.2

A femtosecond pulse train of period trt and its corresponding spectrum,3

a frequency comb of spacing frep = 1/trt . The carrier-envelope phaseslip ∆φCE between adjacent pulses is seen as the time-domain offset
between the carrier oscillations and the pulse envelope. It is connected toa frequency-domain offset f0 = frep ∆φ2πCE (see text) of the frequency-combfrom zero. This illustrates the importance of this parameter both forfrequency measurements and strong-field phenomena such as attosecond
control of electron dynamics. Adapted from [76]. . . . . . . . . . . . . .
1.3

5

Femtosecond near-infrared light source for the experiments in this thesis.
A pulse train from a femtosecond oscillator is amplified using chirped
pulse amplification: pulses are stretched to ∼ 200 ps duration before amplification by a factor > 106 , and then recompressed to ∼ 30f s. The
limited bandwidth of amplified pulses requires further spectral broadening in a ”self-phase modulation” fiber to produce ∼ 10f s pulses. . . . .

1.4

7

Spectrogram (taken with a Grenouille apparatus) corresponding to an
amplified NIR pulse passing through a self-phase modulation fiber. The

1.5

Fourier transform limit corresponds to 6.4 fs. . . . . . . . . . . . . . . .

8Schematic for the generation of extreme ultraviolet radiation. . . . . . .

10

xv
1.6

Representative classical electron trajectories in a laser field.

. . . . . .

1.7

Blue: Kinetic energy of the electron returning to the ion, in units of the13

ponderomotive energy Up . Black: Return phase. Red: Return phase ionization phase. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.8

14

Logarithm of electron position w.r.t. ion core, versus the initial phasewhen the electron is ionized (x-axis), and versus its return phase (yaxis). Light red / yellow: electron position close to the ion core. Dark
red: far from the ion core. . . . . . . . . . . . . . . . . . . . . . . . . . .

1.9

15

Simulations of EUV generation by I. Christov [22], based on numericalsolution of the time-dependent Schroedinger equation. A long fundamental pulse duration τp results in an attosecond EUV pulse train. A shortfundamental pulse can result in an isolated attosecond pulse. . . . . . .

19

1.10 Dynamic phase-matching effects in EUV generation. (a) intensity envelope of a 13 fs fundamental pulse. (b) electric field (blue) and ionization
fraction of the Argon gas (red). (c) phase mismatch for the 25th harmonicin 10 torr of Argon (red), summed-up intensity of 19th − 31st harmonicfrom 25 mm of Argon gas, calculated with the simple model (1.14), withthe additional constraint that only fundamental intensities above the cutoff (1.8) contribute to each harmonic. EUV emission does not peak at
the fundamental intensity maximum but earlier: At late times >∼ −5
fs EUV emission is suppressed by the large phase mismatch due to fullionization of the gas, while at early times it is constrained by the low
fundamental intensity. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

23

1.11 Basic energetics of EUV (energy hν) photoionization (green) and pho-

2.1

todissociation (red) of molecules. . . . . . . . . . . . . . . . . . . . . . .

26

f-2f interferometer used to lock the CEP of the amplifier seed oscillator.

37

xvi
2.2

Phase-locked loop electronics used to stabilize the CEP slip of the oscillator. 39

2.3

Measurement of f0 . (a) shows the RF spectrum recorded with the ”f0 ”
photodiode. (b)-(d) Zooming in on the CEP beat signal. (e) In-loop noise
on a log-scale representation at frequencies > f0 . The feature below 10
Hz corresponds to the resolution bandwidth limited coherent spike, i.e.
it is not a measure of true noise. . . . . . . . . . . . . . . . . . . . . . .

2.4

Measurement of the in-loop oscillator CEP noise using a FFT spectrum
analyzer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.5

44

Comparison of CEP fluctuations a) passing through the SC, b) bypassing
the SC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.7

41

Setup for CEP characterization of a grating-based stretcher-compressor
system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.6

40

47

Measurements of carrier-envelope phase-fluctuations ∆ΦCE , power fluctuations ∆Prms and the ratio of both, when beam pointing fluctuations∆α are introduced. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.8

2.9

49

Electronics that provide a train of CEP-identical seed pulses to the amplifier. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

52

Schematic of the CEP stabilized laser amplifier system. . . . . . . . . .

55

2.10 Spectral interferometry for the measurement of amplifier carrier-envelope
phase fluctuations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

56

2.11 Top, fringe visibility versus integration time of the detector for CEPlocked and CEP-unlocked oscillators. Bottom, accumulated rms CEP
corresponding to a locked oscillator. . . . . . . . . . . . . . . . . . . . .

57

2.12 Evolution of the fringe pattern derived from the output of the amplifier
as a function of time, when (top) the oscillator is phase locked and when(bottom) a sinusoidal voltage is applied to the oscillator locking electronics. 58

xvii
2.13 Correlation between intensity drop of the beat note from the microstructure fiber used in the oscillator feedback loop and drift of the spectralinterference fringes recorded after the amplifier. The intensity drop in
the beat note leads to a deterioration of the feedback loop performance.

59

3.1

Different regimes of laser assisted photoelectron emission. . . . . . . . .

71

3.2

Photoelectron momentum shifts in the presence of fundamental laser light. 72

3.3

Determination of EUV pulse structure from photoelectron spectra in theattosecond streak camera measurement. . . . . . . . . . . . . . . . . . .

74

3.4

Basic schematic of GP algorithm. . . . . . . . . . . . . . . . . . . . . . .

80

3.5

Schematic of GP algorithm adapted to wide-angle photoelectron detection geometry and non-CEP stabilized driving laser pulses. . . . . . . .

3.6Taken from Varju et al. [167]: Harmonic and atto chirps in frequency
and time domain. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.7

82

86

Experimental setup for EUV pulse generation and temporal characterization via photoelectron energy resolved two-color cross-correlation using
a NIR pulse. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

87

3.8

Magnetic bottle time of flight spectrometer. . . . . . . . . . . . . . . . .

89

3.9

Magnetic fields of the time-of-flight photoelectron spectrometer. . . . . .

90

3.10 Electronics following the photoelectron spectrometer setup. . . . . . . .

92

3.11 Labview interface for automated acquisition of photoelectron spectrograms in Windows XP. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

93

3.12 Photoelectron spectrogram demonstrating the good resolution of the spectrometer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

93

xviii3.13 Experimental photoelectron spectrum as a function of time delay between the EUV and NIR pulses, when these pulses are focused simultaneously into He gas. (b) FROGCRAB simulation of the data in (a). (c)FROGCRAB trace obtained from a generalized projections (GP) algorithm. (d) EUV spectrum of the pulse that generated the photoelectron
spectrum shown in (a), independently taken with an x-ray spectrometer96

3.14 Simulated FROGCRAB data, when higher dispersion orders are artificially introduced into the EUV field. . . . . . . . . . . . . . . . . . . . .

97

3.15 (a-c) RMS deviation between the FROG CRAB simulation and the experimental cross-correlation trace as the parameters of the simulated pulse
are varied. (d) experimental FROG CRAB data, (e) FROG CRAB data
simulated using the optimized EUV pulse parameters.(f), (g) simulated
FROG CRAB data using the optimized values of D2, D3 but when the
EUV pulse envelope is changed from the optimized value of 1.4 fs to 1 fs
and 2.5 fs respectively. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

99

3.16 a) Chirped EUV electric field envelope vs. time. b); magnitude (solidblue) and phase (solid blue) retrieved from a GP algorithm; (dotted red)transform limited pulse for comparison. (b) (Solid blue, dashed green):
EUV intensities vs. time corresponding to the chirped pulses shown in(a); (dash-dotted green): intensity of a double pulse with the same envelope; (dotted black) intensity envelope of the extracted EUV field. . . . 100
3.17 EUV spectrum recorded with an x-ray spectrometer (black), and corresponding photoelectron spectrum upshifted by the ionization potential(red). The difference in spectral shape is due to EUV mirror reflectivity(which is low at the lower photon energies). . . . . . . . . . . . . . . . . 103
3.18 Retrieval of a partial FROG CRAB trace. . . . . . . . . . . . . . . . . . 104

xix
3.19 (a) Zoom-in on the experimental photoelectron energy resolved two-color
cross-correlation shown in Fig. 3.18. (b) FROG CRAB trace retrieved
using the GP algorithm. The gate function was thoroughly optimized byrunning the algorithm multiple times to find the gate parameters which
overall minimize the G error. The optimized gate uses a 15 f s fundamental Gaussian pulse with Up = 0.3 eV and a linear chirp of Γ2 = 0.0178 f s2 .
(c) Reconstructed EUV electric field envelope and temporal phase. (d)Reconstructed EUV intensity yielding a FWHM pulse duration of 210
attoseconds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3.20 Simulations for (a) averaged CEP, (b) CEP = 0, (c) CEP = π, (d)retrieved EUV field envelope and phase, (e) intensity of 200 attoseconds
FWHM pulse duration. . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.21 (a) Experimental data of a complete FROG CRAB trace (b) Simulationsof experimental data shown in (a), used to extract NIR fundamental pulse
parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.22 Simulations of chirped attosecond pulse trains. Top row center: experimental data for comparison. Γ2 : femtochirp parameter in 1/f s2 . τe : envelope of the simulated EUV pulse trains (see insets). First row: τe = 1
fs corresponds to an isolated attosecond pulse with two, 10−3 intensityside bursts. τe = 1.5 fs: two, 5% intensity side bursts. All simulated
traces with τe > 1.5 fs show significantly more spectral modulation thanthe experimental data. Simulated traces have been convoluted with theexperimental photoelectron spectrometer resolution function. . . . . . . 110
3.23 Simulations of FROG CRAB traces for different number of EUV bursts.
Left column: CEP stabilized traces; middle column: CEP unstabilized
traces obtained by averaging over CEP 0 and π; right column: EUV
intensity of input pulses. . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

xx
3.24 Comparison of (a) experimental data, (b) GP algorithm, and (c) direct
simulations of FROG CRAB traces using optimized EUV pulse parameters.112
3.25 (a) EUV cutoff harmonic as a function of time, determined from instantaneous intensity. (b) phase mismatch [135, 54] for the 25th harmonic versus
time for straight fiber (red), effect of employing a QPM fiber for same
pulse parameters (blue). Horizontal dashed lines: region of experimentally generated EUV spectrum. Vertical dashed lines: guides to the eyehighlighting the half-cycles in which efficient EUV generation is possible:
Earlier, the instantaneous intensity is too low to generate the experimental spectrum (lower harmonics are absorbed in the generating Argon gas,and not reflected by EUV mirror). Later, large phase mismatch preventscoherent build-up of EUV radiation. . . . . . . . . . . . . . . . . . . . . 114
3.26 Phase matching conditions for ionization gating. Phase-matching-criterion
for the time window in which the 21st-29th harmonics are first generated as a function of the laser peak intensity and gas pressure for (a)CEP = π/2 (b) CEP = 0. Warmer colors represent better phase matching. The corresponding temporal overlap of the laser pulse at the end of
the medium (red) over the pulse at the beginning of the medium (blue)is shown in (c) and (d). . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.1

Artist’s impression of molecular photoionization. . . . . . . . . . . . . . 122

4.2

The COLTRIMS setup. A light source is focused onto a gas jet in thecenter of the apparatus. The ion (blue trajectory) and electron (redtrajectory) are guided to opposite time-and position sensitive detectors(red, blue) by electric and magnetic fields. Taken from [1]. . . . . . . . . 123

xxi
4.3

Setup of the supersonic gas jet. (a) green: the skimmer, located above
the nozzle in which supersonic expansion and cooling occurs, transmits
the central, transversely cold region of the jet, to the interaction region
above. (b) gas delivery setup, and catcher (top). . . . . . . . . . . . . . 125

4.4

Schematic of a supersonic gas jet . . . . . . . . . . . . . . . . . . . . . . 126

4.5

Ionization events from gas jet (intense spot) and background gas (diffuseband). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127

4.6

Magnetic field calibration using ”fish” images (transverse electron hit
position Yrot versus time of flight). . . . . . . . . . . . . . . . . . . . . . 131

4.7

The DLD detector. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132

4.8

The HEX detector. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

4.9

Definition of molecular polarizabilities α|| along and α⊥ perpendicular to
the molecular axis. The alignment field E torques the molecule towards
the field axis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137

4.10 Schematic of impulsive molecular alignment. . . . . . . . . . . . . . . . . 138
4.11 Calculated alignment cosine for N2 versus time after alignment pulse.
Left: dependence on alignment pulse intensity at fixed rotational temperature. Right: dependence on temperature at fixed alignment pulse
intensity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
4.12 Experimental setup for the measurement of the angular dependence ofphotoionization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
4.13 Photoelectron spectra in coincidence with (a) N2+ (red) and N + (blue)(b) CO2+ (red) and O+ (blue).

. . . . . . . . . . . . . . . . . . . . . . . 153

4.14 EUV ionization yields from transiently aligned N2 . Extracted angulardependence of the EUV photoionization cross section to N2+ and N2+
dissociative states (N + ). . . . . . . . . . . . . . . . . . . . . . . . . . . . 154

xxii
4.15 EUV ionization yields from transiently aligned CO2 . Extracted angulardependence of the EUV photoionization cross section to CO2+ and CO2+
dissociative states (O+ ). . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
4.16 Lab frame momentum distribution of photoelectrons from N2 . . . . . . . 162
4.17 Difference in photoelectron angular distributions for aligned (a) and antialigned (b) molecules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
4.18 Coordinates used for the description of molecular-frame photoelectron
angular distributions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
4.19 Time of flight spectrum of all charged fragments of N2 O irradiated with
43 eV light. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
4.20 Coincidence filters applied. Left: unfiltered T OF2 vs T OF1 image of two
ion fragments detected in coincidence from the fragmentation of N2 O.
Right: The Coulomb-explosion channels of interest, N2 O → N O+ + N +and N2 O → N2+ + O+ are selected out by a filter relating T OF2 andT OF1 via the momentum conservation in the Coulomb explosion. . . . . 167
4.21 2D projection of the momentum image of N O+ from the Coulomb explosion N2 O → N O+ + O+ . . . . . . . . . . . . . . . . . . . . . . . . . 168
4.22 The momentum image of O+ following dissociative ionization of O2 shows
4 dissociation channels, 1: O+ (2 P) + O(3 P), 2: O+ (4 S) + O(3 P), 3:
O+ (4 S) + O∗ (1 D), 4: O+ (4 S) + O(3 P). . . . . . . . . . . . . . . . . . . 169

Chapter 1
Introduction

The work in this thesis involved several topics ranging from the generation andtemporal characterization of coherent ultrafast extreme-ultraviolet (EUV) radiation to
its application in molecular physics. The fundamental light-matter interaction leading
to the generation of this EUV radiation is the recollision of an electron with its parent
ion after it was ejected and accelerated by an intense near-infrared laser field. In thisrecollision, the electron may give up its energy and emit a high-energy photon. This
basic process has allowed the realization of table-top EUV sources which provide laserlike radiation with unique properties: femtosecond to attosecond pulse duration, good
spatial and temporal coherence, energy-tunability, and temporal synchronization withthe driving laser pulse which is essential for pump/probe experiments. The accessibleenergy range is suitable for probing outer and inner valence level (and not-too-tightly
bound core level) atomic / molecular physics, as well as for studies of condensed mattersystems. A very recent achievement is the generation of EUV pulses of sub-optical cycle
duration, or even a single isolated attosecond EUV burst per laser pulse - the shortest
manmade events to date. Isolated attosecond pulses have been produced either by anextremely short driving laser pulse, by driving pulses with time-varying polarization, or- as implemented for the first time in this thesis - by exploiting dynamic phase-matchingeffects between the driving laser and EUV pulse.

2

1.1

Background: Relevant Time Scales
Why are we interested in experimentally making attosecond timescales accessible?

Ever shorter pulse durations allow us to make movies with unprecedented time resolutionof ever faster processes occurring in nature. In the past this has led to time-resolved
observations of nuclear motions, such as in molecular rotations, which happen on apicosecond timescale (1 ps = 10−12 seconds) or in molecular vibrations, which happen
on a femtosecond (1 f s = 10−15 seconds) timescale, as well as in chemical reactions
which evolve on a similar timescale as vibrations [179].
One challenge remains: Similar movies of electronic processes in inner atomic
shells prove much more difficult, as these motions take place over tens to thousands ofattoseconds (1 as = 10−18 seconds), e.g. the electron-orbit period for the ground stateof the hydrogen atom is 150 as. Within the past years, scientists have begun to learn
how to use femtosecond laser pulses to coherently manipulate electron motions in atoms
and molecules, down to attosecond timescales. With the beginning of this new era of attosecond science, we now have the possibility of manipulating and measuring electronic
wavefunctions. In addition to purely electronic motions, a very interesting regime of
motions occurs on the order of a few femtoseconds: When the Born-Oppenheimer approximation 1 breaks down, the nuclear and electronic dynamics become coupled, as
it occurs at conical intersections between molecular electronic potential surfaces. An
overview of the timescales relevant to this thesis is given in Figure 1.1.
By the uncertainty principle, sub-femtosecond light pulses require a bandwidth
larger than 1015 Hz, which is larger than the entire visible range of the spectrum. Therefore, to generate attosecond timescale radiation it is necessary to work with higher frequency radiation. High harmonic generation from intense near-infrared laser pulses can
1
The Born-Oppenheimer approximation is often made in molecular physics. It assumes that electrons
adjust their positions much faster than any motion of the nuclei. Within this adiabatic approximation
the electronic energy eigenvalues can then be displayed as a function of nuclear distances aka potential
energy surfaces.

phonons

optical cycle@ 800nmmolecular
vibrations

Auger
lifetimes

10-12

seconds
molecular
rotationsplasmons

10-15
coupled electronic &nuclear motions(conical intersections)

EUV cycle@ 30nmelectronmotionin atoms

10-18

3

Figure 1.1: Time scales of matter and light relevant to this thesis.

certainly access these timescales. However it should be noted here, that manipulationof electron dynamics on the attosecond time scale does not require the use of isolated
attosecond pulses. As an example, pulse shaping techniques of intense NIR femtosecond
pulses can be used to manipulate electron trajectories in the continuum with a precisionof 25 attoseconds [11].

1.2

Overview of work in this thesis
The temporal characterization, as well as many applications of ultrafast EUV

radiation are typically done by a two-color cross correlation with the fundamental light,
and detected by making use of the ionizing nature of the radiation. In this thesis, I
have set up a beamline for the generation and temporal characterization of EUV pulses,
including a hollow-waveguide setup for high-harmonic generation, a piezoelectric delay
stage with attosecond resolution, and a photoelectron spectrometer allowing efficient2 − π photoelectron collection. I have generated and temporally characterized two
different regimes of EUV radiation, producing 1.4 femtosecond (fs) pulses as well as 200
attosecond (as) pulses. The 1.4 fs pulses will be particularly useful, because they are4close to the Fourier transform limit, meaning in addition to their short pulse duration we
have sufficient energy resolution (∼ 1 eV) for state resolved experiments in the congested
molecular and materials energy bands in the EUV region. This regime also distinguishes
itself by a high photon flux and easy energy tunability due to phase-matching in thehigh harmonic generation waveguide. The 200 as pulses have a correspondingly broader
spectrum, and will thus have their applications in the study of even faster processes
where state-selectivity is not required.
In the next project I used few-femtosecond EUV pulses in combination with the
COLTRIMS detection technique for a basic molecular physics experiment: The measurement of the angular dependence of molecular photoionization. The experiments
are performed in the gas phase, requiring an initial alignment step. Alignment is performed by impulsively torquing the molecules using a near-infrared femtosecond pulse.
This new technique allows to study non-dissociative ionizations and dissociations thatinvolve long-lived intermediate states, as we showed for dissociation of CO2 at 43 eV
excitation energy which likely proceeds through the long-lived C 4σg channel of CO2+ .
At the beginning of this PhD a high-power femtosecond pulse train was realized
which had its electric field oscillations stabilized underneath the pulse intensity envelope. Such carrier-envelope phase (CEP) stabilized amplified pulses will have many
applications in strong-field physics and attosecond science.
In the following I will thus give an introduction to the topics of generation, temporal characterization and applications of ultrafast EUV radiation, as well as the CEP
stabilization of high-power fs lasers.

1.3

A carrier-envelope phase (CEP) stabilized amplifier
The objective of the first project of my PhD work was to develop a laser systemcapable of generating high-power femtosecond laser pulses with a stable phase of theelectric field oscillations under the pulse envelope (carrier-envelope phase, CEP, see5Figure 1.2). In conventional femtosecond laser pulse trains from a Ti:Sapphire oscillator(and thus also in amplified pulse trains seeded by such oscillators), the repetition period
and the pulse envelope are stable in time. However the CEP is random from one
pulse to the next, due to the differing group and phase velocities in the laser cavity.
Highly nonlinear processes, such as EUV generation or other strong-field phenomena,
can be very sensitive to the fluctuations of the CEP. For example, when very shortdriving pulses are used for high harmonic generation, the properties of the emitted
EUV pulse can depend very sensitively on the position of the electric field oscillationsof the fundamental pulse, not just on the envelope. A ”cosine” driving pulse with onestrongest half-cycle will generate a single attosecond pulse, whereas a ”sine” driving
pulse with two equally strong half-cycles will generate two attosecond pulses.
femtosecond pulse train

corresponding spectrum

Figure 1.2: A femtosecond pulse train of period trt and its corresponding spectrum, afrequency comb of spacing frep = 1/trt . The carrier-envelope phase slip ∆φCE between
adjacent pulses is seen as the time-domain offset between the carrier oscillations and thepulse envelope. It is connected to a frequency-domain offset f0 = frep ∆φ2πCE (see text) of
the frequency-comb from zero. This illustrates the importance of this parameter bothfor frequency measurements and strong-field phenomena such as attosecond control ofelectron dynamics. Adapted from [76].

6
The technique of stabilizing the CEP to a fixed value is nowadays reasonably
straightforward for femtosecond oscillators [76]. However an oscillator only produces
pulse energies on the order of a few nanoJoules. To reach intensities required e.g. togenerate EUV light, an amplification by a large factor (∼ 106 ) is needed. A typicalsetup to achieve this uses the principle of chirped-pulse amplification [148] (see figure1.3). For the CEP stabilization of such amplifier systems additional complications arise,
which had to be addressed.

1.3.1

CEP stabilization of low-power femtosecond pulses

For low-power oscillator pulse trains there is a convenient way of detecting andcontrolling this phase slip in the spectral domain, as indicated in Figure 1.2. The
spectrum of the pulse train consists of a mode comb, which has two degrees of freedom.
The first is the offset frequency f0 of the comb, which arises from dispersive elements inthe laser cavity. The other degree of freedom is the repetition frequency frep , determinedby the pulse round trip time in the laser cavity. For oscillator pulse trains this repetition
rate is high enough to spectrally resolve the offset frequency. As will be shown in
Chapter 2, the ratio f0 /frep determines the CEP pulse-to-pulse slip according to f0 =frep ∆φ2πCE . By locking this ratio of two measurable radio-frequencies, the electric fieldunder the envelope is fixed. Although we do not know the absolute CE-phase, there arephysical phenomena that depend on this absolute phase, and therefore it is in principle
possible to detect and control it. Examples include the work of Paulus et al. using
above-threshold photoionization [118, 119], and the work in the Cundiff group on CEPdependent photocurrent generation in semiconductors [132].

1.3.2

CEP stabilization of amplified ultrafast laser pulses

Figure 1.3 shows the generation of amplified femtosecond pulses by chirped-pulse
amplification (CPA). A seed oscillator produces ∼ 4−9 nJ, ∼ 25 fs pulses. Amplification

7!     

    noble gas filled hollow waveguide (1m)    

spectral broadening
chirped mirrors
pulse compression~10fs, 0.7mJ

Figure 1.3: Femtosecond near-infrared light source for the experiments in this thesis. A
pulse train from a femtosecond oscillator is amplified using chirped pulse amplification:pulses are stretched to ∼ 200 ps duration before amplification by a factor > 106 , andthen recompressed to ∼ 30f s. The limited bandwidth of amplified pulses requires
further spectral broadening in a ”self-phase modulation” fiber [113, 149] to produce∼ 10f s pulses.

proceeds via temporally stretching the pulses from ∼ 20 fs to ∼ 200 ps duration in astretcher. This is required to avoid material damage in the amplifier gain medium. A
Pockels cell selects pulses at a ∼ 1 kHz repetition rate for amplification. The stretchedpulses are amplified to ∼ 3 mJ in a multipass cryo-cooled amplifier ring, and are thenrecompressed to 1 − 2 mJ per pulse, ∼ 30 fs in the compressor before being sent to the
EUV generation setup. For some experiments the limited bandwidth of amplified pulses
requires further spectral broadening in a self-phase modulation fiber to produce ∼ 10 fs
pulses. Figure 1.4 shows a spectrogram of ∼ 10 fs pulses exiting the SPM fiber, takenwith a Grenouille apparatus used for routine temporal characterization of NIR pulses.
For stretching/compression in chirped pulse amplification there are two methods, which both introduce a frequency-dependent delay to stretch the pulse: material
based stretcher-compressors and grating based stretcher-compressors. In material based
stretcher-compressors, highly dispersive glasses are used for stretching, and pulse energies are limited to about 3 mJ. Grating based stretcher-compressors, on the other hand,
introduce frequency-dependent beam paths in free space, and are scalable to ∼ 1000

8

Figure 1.4: Spectrogram (taken with a Grenouille apparatus) corresponding to an amplified NIR pulse passing through a self-phase modulation fiber. The Fourier transform
limit corresponds to 6.4 fs.

times higher pulse energies. For the first demonstration of amplification of CEP stablepulses, material based stretcher-compressors systems were used, while the grating-based
stretcher and compressors used in our group had been predicted to be at a disadvantage for CEP stabilization, due to a strong conversion of beam-pointing fluctuations
to CEP noise. Our strategy was thus to first investigate this claim by characterizing
the CEP noise introduced in a separate stretcher/compressor system without the actual
amplifier. Once we had shown that the introduced CEP noise was negligible, the full
amplifier was set up and CEP stabilized.
For an amplifier with much lower repetition rate than an oscillator, the offset
frequency f0 is not readily resolvable, and another technique has to be used to detect
the CEP and stabilize the pulse train: In this work we used spectral interferometry,a technique that encodes the CEP slip in a spectral offset of an interference pattern

9
as I will show in chapter 2. Using this technique, we could demonstrate the intrinsic
long-term CEP stability of our grating-based amplifier system.
In the early demonstrations of CEP stabilized amplifiers, stabilization is achievedby pre-compensating slow CEP fluctuations from the amplifier using actuators in theseed oscillator. In another more recent technique, slow CEP feedback control of anamplifier was demonstrated using feedback on the effective stretcher grating separation[94]. In the years since our own work was completed, the field of CEP stabilized amplifiers has continued to make great progress. CEP stabilized amplifiers up to several
milliJoules are now commercially available. Nonetheless the use of CEP stabilized amplifiers will continue to be challenging due to the requirement of ensuring low levels ofelectronic, acoustic and vibrational noise in the lab.

1.4

Generation of coherent ultrafast extreme-ultraviolet radiation
As EUV generation is the basic tool for most experiments in this thesis, I will

give here an overview of its generation. To understand EUV generation two points
have to be considered: The first point is the single-atom description, which provides
an understanding of the temporal structure, as well as a first estimate for the energy
range of EUV emission. The second point is the macroscopic emission of an ensemble ofatoms, where coherence between different emitters decides on the spatial and temporal
coherence properties, the directionality of the emission, the overall signal strength, andalso the final temporal structure of the macroscopic radiation.

1.4.1

The three-step model

An intuitive semiclassical model for the interaction of the intense laser field ofa femtosecond pulse with atoms, leading to high harmonic generation, was given by
Corkum [26] – the ”three-step model” (see Fig. 1.5). When an intense laser pulse isfocused onto atoms in the gas-phase, it may suppress the Coulomb potential sufficiently

10

Figure 1.5: Schematic for the generation of extreme ultraviolet radiation: infrared radiation is focused into a gas target, leading to laser-like emission of EUV in the forward
direction. Blue: in the three-step model of HHG, an electron is set free by tunnel
ionization, and is then accelerated by the laser field gaining kinetic energy. When it returns to the nucleus it may recombine and emit EUV radiation. Lower panel: quantum
mechanical simulations of electron wave packet propagation. In this picture of HHG
the rapid spatio-temporal interference between returning electron wave packet and the
portion remaining close to the nucleus generates a radiating dipole. From [82].

for electrons to tunnel. Thus, near each peak of the electric field of a femtosecond laser
pulse a portion of an electron wave packet is set free from an atom through tunnel
ionization. In this first step the probability of ionization as a function of the laser
electric field is calculated using the ADK tunnel ionization model (see Section 1.4.1.1).
The second step describes the classical electron trajectory after ionization, accelerated
by the electric field of the fundamental pulse. In a linearly polarized laser field there isa significant probability for the free portion of the electron wave packet to reencounterits parent ion. In this third step, EUV radiation is emitted when the free portion of the
wave packet recombines with the remaining part of the ground state wavefunction.
This EUV emission has a temporal periodicity of half the laser cycle (TL /2), that

11
follows the electric field strength of the fundamental laser pulse, generating an EUV
attosecond pulse train. This in turn leads to a discrete spectral structure of the emitted
radiation with a frequency spacing of twice the laser frequency (2ωL ). Only odd harmonics are emitted because of a constraint on the n’th order nonlinear susceptibility χ(n)in an isotropic gas: if the direction of the electric field is reversed, E → −E, then alsoP
the polarization of the gas must reverse its sign: P → −P . Because P = ²0 n χ(n) E n ,only odd orders χ(2m+1) are allowed and only odd harmonics are generated.
In the following I will describe in detail the three steps of the model, as well assome of the most important predictions.
1.4.1.1

Step 1: ADK-model for the electron tunneling probability

A strong laser field suppresses the Coulomb potential, so that the electron may
tunnel out of its potential well, or even escape over the barrier for sufficiently strong
suppression. The tunneling probability T is
!¯2
Ã Z r
¯
µ Z b
¶¯2 ¯¯
¯
b
¯
¯
2m(I
−
V
(x))
¯
¯
p
T = ¯¯exp −kdx ¯¯ = ¯exp −
dx
¯
2
¯
¯
~
a
a

(1.1)

Here, k is the wave vector of the tunneling electron, a and b are the inner and outeredges of the tunnel barrier, V (x) is the combined Coulomb and laser potential and Ip
is the atom’s ionization potential. To convert the probability into an ionization rate
Rion (t) one multiplies by the attempt frequency, given e.g. in the Bohr model by twice
the binding energy (or ionization potential) 2Ip /~.
The ADK model describes the ionization rate Rion (t) in a strong electric field
E(t) [145, 26]:
s
n∗ =
∗

IpH
Ip

2
Cnl
= 22n /(n∗ Γ(n∗ + 1)Γ(n∗ ))√√µ¶(2n∗ −1)µ¶
Ip 2 4Ip 2mIp
4Ip 2mIp
Rion (t) =
C
exp −
~ nl
~e|E(t)|3~e|E(t)|

(1.2)
(1.3)
(1.4)

12
Here, m and e are the electron’s mass and charge, respectively, Ip and IpH are
the ionization potential of the atom of interest and the hydrogen atom, respectively,and Γ is the Gamma function. This expression shows that ionization is strongly peakedaround the maxima of the electric field. As we will see in step 2 of the model, theionization time decides on the energy E available for EUV emission.
The time-dependent ionization rate Rion (t) also leads to a time-dependent plasma
fraction η(t) that increases during each half-cycle of the femtosecond laser pulse:
µ Z t
¶
0
0
η(t) = 1 − exp −dt Rion (t ) .

(1.5)

−∞

This ionization fraction is important for dynamic phase-matching effects thatallow the generation of single isolated attosecond pulses, as will be shown below.
Note that more advanced models of ionization [24] take into account nonadiabatic
effects, leading for pulses shorter than ∼ 25 fs to lower ionization rates than predicted
by Eq. 1.4.
1.4.1.2

Step 2: Classical trajectories

From the time of tunneling, the electron is accelerated by the laser electric field.
It is first driven away and when the electric field switches sign, it is accelerated backtoward the nucleus. The motion is described by Newton’s equations, and the solutions
are given in [26]. Figure 1.6 shows three representative trajectories as a function ofphase ωt where ω is the laser angular frequency. 0 degrees corresponds to a maximumof the electric field. The black trajectory, ionized at a phase φion = ωtion = 17◦ , returns
to the nucleus with maximum slope (velocity), generating the highest EUV energy
possible. For all lower return energies, there exist two distinct electron trajectories
returning to the nucleus with the same kinetic energy (and therefore generating thesame harmonic). These are referred to as the ‘long’ and ‘short’ trajectories (red andblue curves, respectively).

13

-2

x / (eE/mω2)

-1.5
-1
-0.5
0

4o 17o 42o

-0.5
-1
0

50

100

150

200

φ=ωt [degrees]

250

300

350

Figure 1.6: Representative classical electron trajectories [26] in a laser field. x = 0 is the
position of the nucleus. The black trajectory, ionized at 17◦ , returns to the nucleus withmaximum slope (velocity), generating the highest EUV energy possible (3.17 Up + Ip )where Up is given by Eq. (1.6). Blue and red trajectories, ionized at 42◦ and 4◦ ,respectively, are representative long and short trajectories returning to the nucleus withidentical energy, in this case generating radiation of ∼ 1.4 Up + Ip . Electrons ionized
between 90◦ and 180◦ (not shown) do not reencounter the nucleus and do not generate
EUV radiation.

A characteristic energy scale in this classical electron motion is the ponderomotive
potential
Up = e2 Ea (t)2 /(4me ωL2 )(1.6)

which is the cycle averaged kinetic energy of the free electron in the electric field EL (t) =Ea (t)cos(ωL t + φCE ) of envelope Ea (t) and frequency ωL . Here, φCE is the phasebetween the oscillations of the carrier frequency and the envelope maximum of thepulse (”carrier-envelope phase”).
Fig. 1.7 shows three plots as a function of the phase of the laser field at which
the electron tunnels. The blue curve gives the return kinetic energy in units of Up .
The black curve gives the return phase, and the red curve shows the difference between
return phase and ionization phase, i.e. the time the electron spent in the continuum.
Ionization for the long trajectories takes place between 0 and 17 degrees and the return

14
350

return phasereturn phase - ionization phase 3
Ereturn / Up

250
2

200
150

Ereturn / Up

φ=ωt [degrees]

300

1

100
50
0

0

20

40
60
φionization=ωtionization [degrees]

80

0Figure 1.7: Blue: Kinetic energy of the electron returning to the ion, in units of theponderomotive energy Up . Black: Return phase. Red: Return phase - ionization phase.

phase is between 360 and 255 degrees. For the short trajectories ionization happens
between 17 and 90 degrees and the return phase corresponds to 255 and 90 degrees.
For the case of an electron ionized at 17 degrees, there is only one trajectory. In thiscase the electron spends a time corresponding to ∼ 238 degrees of laser phase in thecontinuum before returning to the nucleus with maximum kinetic energy, just before
the sign of the electric field switches again to decelerate it.
Fig. 1.8 shows a logarithmic plot of the modulus of the electron position withrespect to the nucleus, as a function of tunnel phase and return phase. The yellow color
corresponds to the electron at the position of the nucleus. It shows that the electron
returns to the nucleus for an initial phase of 0 to 90 degrees, but never returns forionization phases larger than 90 degrees and smaller than 180 degrees. Therefore, noharmonics will be generated from electrons ionized between 90 and 180 degrees. Afterhalf a fundamental laser cycle the process repeats.
As can be seen from Figure 1.7, the ionization time ti decides on the energy E
available for EUV emission when the electron recollides. The ionization rate Rion (t) can

15
700

600

return phase [deg]

500

400

300

200

100

100

200

300
400
initial phase [deg]

500

600

700

Figure 1.8: Logarithm of electron position w.r.t. ion core, versus the initial phase whenthe electron is ionized (x-axis), and versus its return phase (y-axis). Light red / yellow:
electron position close to the ion core. Dark red: far from the ion core.

therefore be converted into a probability dP (E)/dE = Rion (ti (E))(dti /dE) telling us
how likely it is that the electron reencounters the nucleus with just the right energy toemit a photon of energy E. What remains to be calculated in step 3 is the probability
that it will actually emit this photon.

1.4.1.3

Step 3: Recombination and EUV emission

When the electron returns to the nucleus, there is a probability for it to recombine
into the ground state and to emit EUV radiation. The emission is calculated from thesecond time derivative of the expectation value of the dipole moment operator, and thespectrum is found by Fourier transform. The wave function is a superposition of a free
portion and a portion remaining in the ground state. Only when < Ψground |er|Ψf ree >is nonzero, radiation will be generated. For Ψground the unperturbed outermost atomic
orbital may be assumed. Ψf ree (t) is the returning electron wave packet. It can be
expanded in a sum over contributions with the right momentum pq to generate harmonic

16order q [26]:Ψf ree (t) =XÃ ÃAq exp(ipq x/~) exp i

q

!
!
p2q
+ Ip t/~2m(1.7)

where the normalization constant Aq depends on the ionization probability for electrons
returning with suitable kinetic energy to create harmonic q, as well as the transverse
spread of the electron wave function of ∼ 1.5 Angstrom/f s.

1.4.1.4

Predictions of the Model

Most importantly, the three-step model correctly predicts the maximum possible
EUV photon energy, which is given by the sum of the atom’s ionization potential Ip andand the maximum kinetic energy [26] the electron can receive from the laser field whenreturning to the nucleus. This cutoff energy of high harmonic radiation is therefore
given by
Ecutof f = Ip + 3.17Up(1.8)

where Up is the ponderomotive energy of the electron in the laser field. The model
predicts that the maximum kinetic energy of 3.17Up (and thereby the high harmonic
cutoff) is gained when the electron is ionized at a phase of the electric field of ∼ 17
degrees with respect to the the field maximum.
The model also predicts the existence of a plateau region where harmonic intensity
remains almost independent of energy. Further, as already indicated in Figure 1.6,
in each half-cycle two trajectories, ‘long’ and ‘short’, contribute to emission of any
particular harmonic, in agreement with experiments.
The three-step model also predicts that even a small ellipticity of the fundamental
polarization rapidly quenches EUV emission [25, 42]. In this case the electron trajectoryis two-dimensional, and the probability of a reencounter with the parent ion is reduced
significantly. This effect is used in the polarization gating technique for the generationof isolated attosecond pulses [25, 74].

17
1.4.1.5

The intrinsic phase of HHG

So far, the model has neglected a correct description of the phase properties ofharmonic emission. During its motion in the continuum, the electron behaves like awave and thus acquires a phase during its motion. When it recombines and emits aphoton, this phase is imprinted on the radiation. These effects were first discussed
by Lewenstein and coworkers [93], leading to a model that has since then successfully
described many experiments [19, 123, 70].
The total phase Φtot of an electron that generates radiation at frequency ω is
Φtot = ω · tr + Φintrinsic(1.9)

It contains a term ω · tr corresponding to the return time, and the phase the electron
accumulates on its trajectory, i.e. the “intrinsic” phaseΦintrinsic = −S(ti , tr )/~(1.10)

Here, ti is the release time of the electron, tr is the return time, and S(ti , tr ) is
the semi-classical action over the electrons trajectory as calculated using Step 2 of thethree-step modelµ

Z tr
S(ti , tr ) =

dt
ti

¶
(p − A(t))2+ Ip
2m(1.11)

Here, p is the canonical momentum and A(t) is the laser’s vector potential. The
semi-classical action S can be approximated as S ≈ Up τ , where τ = tr − ti is the time
between tunneling and recombination [137].
Equation 1.9 can be used to calculate the spectral phase properties φ(ω) of EUV
radiation, by evaluating it for the trajectories contributing to emission at frequency ω.
An important consequence of Eq. (1.11) is that the phase properties of EUV radiation
can be manipulated during the few-femtosecond trajectory of the electron driven by thelaser field, e.g. by shaping the laser pulse [11].

18
1.4.2

Advanced single-atom models for HHG

Alternatively to using the three-step model based on ADK tunneling theory, classical electron trajectories, and recombination, or the Lewenstein model, one can describe the HHG process quantum mechanically, e.g. numerical simulations of the timedependent Schroedinger equation [160]. The time-dependent electron wavefunction is
calculated by split-step Fourier techniques. The dipole acceleration calculated from thetime-dependent wavefunction then gives the EUV emission amplitude in time; Fouriertransform to frequency domain gives the HHG spectrum.
To achieve the generation of a single attosecond pulse within a single-atom modelof high-harmonic generation, the laser pulse must be short enough so that only few laser
cycle peaks give rise to high harmonic generation (HHG). Then a single attosecond pulse
can be isolated by spectrally filtering the highest energy radiation [22]. For longer pulses
the EUV emission forms an attosecond pulse train with a temporal periodicity of T0 /2.
This temporal periodicity leads to a discrete spectral structure of the emitted radiation
with a frequency spacing of 2ωL . This is shown in Figure 1.9.
However single-atom effects in general are not always sufficient to describe EUV
generation. The next section describes how single-atom predictions will be modified
by macroscopic effects. These macroscopic effects offer new routes to attosecond pulse
generation.

1.4.3

Macroscopic effects on HHG emission: Phase matching

The macroscopic EUV radiation generated from many emitters can be different
from the single-atom radiation due to propagation effects, such as phase-matching andabsorption. These effects can be tailored to manipulate the properties of the emitted
radiation.
If atoms should emit EUV radiation constructively over a long interaction length

19

Ionization

τp= 100 fs

Harmonic
emission
fundamental
E field

τp= 25 fs

τp= 5 fs

0

5

10

15
20
Time(fs)

25

30

Figure 1.9: Simulations of EUV generation [22], based on numerical solution of thetime-dependent Schroedinger equation. A long fundamental pulse duration τp results
in an attosecond EUV pulse train. A short fundamental pulse, combined with spectral
filtering, can result in an isolated attosecond pulse.

in a macroscopic generation medium, as e.g. in a hollow core waveguide, one mustensure that the harmonic radiation travels with the same phase velocity through the
waveguide as the fundamental pulse. Such phase matching conditions can be effectively
implemented in a gas-filled hollow-core waveguide, because the waveguide can tightly
confine the light and enforce plane-wave propagation over a macroscopic length. By
modifying the structure of the waveguide (e.g. using a tapered or corrugated waveguide)
additional phase matching terms can be introduced [23, 116].
The phase mismatch between the q’th harmonic and the fundamental light isgiven by∆k(t) = q · klaser (t) − kq

(1.12)

where kq is the wave vector of the q’th harmonic, and klaser (t) the fundamental laser

20wave vector. A general expression for the wave vector of light in a waveguide filled withgas is given by [135]k(t) ≈ 2π/λ +

2πN (1 − η(t))δ(λ)
u2 λ− N η(t)re λ − nm 2λ
4πa(1.13)

Here, N is the total gas density (neutral gas plus plasma), η(t) is the time-dependent
ionization fraction (calculated using equation 1.5), δ(λ) describes the dispersive characteristics of the atom, re is the classical electron radius, a is the waveguide radius, andunm is the mth root of the (n − 1)th Bessel function of the first kind and depends on
the transverse modes coupled into the waveguide. One finds that the influence of the
waveguide and the plasma on the phase mismatch is q 2 smaller (λq = λf und /q). Also theneutral gas dispersion δ(λ) is in general small at x-ray wavelengths. The EUV radiationis thus not strongly affected by any of the three dispersion contributions, and its wave
vector kq in Eq. (1.12) is only slightly modified from its vacuum value.
If phase-matching is fulfilled, the generated radiation will interfere constructively
along the whole generation region (limited only by absorption, see below). The intensity
increases quadratically with the number of emitters. For EUV generation in a gas-filled
waveguide we therefore get a quadratic dependence of phase matched emission with fiber
length. On the other hand if ∆k 6= 0, the signal will start to interfere destructively afterπ
a coherence length defined by Lcoh = ∆k
. Coherence lengths for HHG in the presenceof high levels of ionization are on the order of µm − mm.
To understand how one can influence the phase mismatch, consider the contributions to the k-vector (1.13). Neutral gas increases the k-vector, the waveguide andthe plasma reduce the k-vector. As the harmonic k-vector is nearly unchanged fromits vacuum value, the fundamental k-vector can be influenced independently to achievephase-matching. For large ionization fractions η, the plasma term becomes dominantand destroys phase-matching (then the neutral gas term becomes small, and the waveguide anyway adds with same sign to the plasma term).

21
Not only phase matching but also EUV absorption can limit EUV generation:
The electric field is attenuated with propagation length L according to Beer’s law E =E0 exp(−αL) (Note: α is defined here as the field absorption coefficient.). A typicalabsorption length L = 1/(2α) is ∼ 30 mm for λ = 25 nm radiation in 10 torr Argon.
Empirically it had been found that the intensity of EUV radiation depends onthe fundamental intensity as IHHG ∝ IF2s , where the effective nonlinearity 2s of thegeneration process is 2s ≈ 11. Durfee et al. [71] combine these three ingredients,
effective nonlinearity, phase matching and absorption, to give an approximate formulafor the EUV output:Ã
IHH (t) ∼ NA2 IF2s(t)1 + exp(−2αL) − 2 exp(−αL) cos(∆k(t)L)
2
α2 + ∆k(t)!
(1.14)The term in brackets reduces to sinc2 (∆kL/2) if absorption is neglected.
Finally we note that in a real waveguide there are several other contributions
that need to be taken into account, such as e.g. a varying coherence length along thefiber due to losses from ionization (and Fresnel reflections) and mode beating of various
coupled spatial modes.

1.4.4

Attosecond pulse generation in a hollow waveguide

Despite being oversimplified, equation (1.14) suggests different ways to achieve asingle isolated attosecond pulse: The high-order IF11(t) dependence suggests that EUV
pulses are significantly shorter than their driving pulses, and that shortening the fundamental pulse to a few femtoseconds should localize EUV generation to less than ahalf-cycle (1.33 fs for 800 nm). Theoretical calculations [22] show that the use of 5
fs pulses, in combination with spectral filtering, allow for generation of an isolated attosecond pulse. However the generation and management of such few cycle pulses istechnically very challenging.
Instead we can focus on the phase-matching contribution to Eq. (1.14) and engi-

22neer some process that limits EUV emission to a temporal window smaller than a halfcycle of the driving fundamental field. The phase mismatch (1.12) has a very strong
time-dependence due to the time-dependent ionization fraction η(t) in (1.13). The fast
sweep of the phase mismatch through zero can be used to generate single attosecond
pulses even from relatively long (∼ 15f s) femtosecond driving pulses.
The upper graph in Fig. 1.10 shows the intensity of a NIR 13 fs driving pulse. (b)shows the corresponding electric field (blue). When sufficient field strength is reached,
the field ionizes the gas in the fiber and creates a plasma. The red line shows how
the ionization fraction in the gas rapidly increases. For the conditions here, nearly fullionization is reached around the pulse peak. The generated plasma gives a negative
contribution to the phase mismatch, which varies rapidly in time. This phase mismatchis shown in red in (c). Initially the neutral gas causes a slight positive mismatch (thenegative waveguide term does not compensate this). The growing plasma contribution
sweeps the phase mismatch to zero and then to large negative values. Also shown in(c) is the summed-up intensity of 19th − 31st harmonic generated from 25 mm of Argongas, calculated with the simple model (1.14), with the additional constraint that only
fundamental intensities above the cutoff intensity for each harmonic, calculated from Eq.
(1.8), contribute. Note that EUV emission does not peak at the fundamental intensity
maximum but earlier. At late times >∼ −5 fs emission is suppressed by the large phasemismatch due to nearly complete ionization of the gas. At early times EUV emission isconstrained by the low fundamental intensity. While this oversimplified model should
not be taken too seriously, it predicts the generation of EUV pulses of order of 1 fs froma 13 fs driving pulse.
If we could now still add a constant offset to the phase mismatch in Fig. 1.10, thenwe could shift the phase-matching window in time toward the pulse peak, and phasematch the highest harmonics. Even more importantly, the sweep of the phase mismatch
through zero can be even more rapid, and create an even shorter temporal phase-

23

14

4x10

14

3x10

14

2x10

14

1x10

14

0

ionization fraction(b)phase mismatch (1/m)

(c)

10

8x10
10
6x10
10
4x10
10
2x10
0

0.8
0.6

10

0.4

-2x10
10
-4x10
10
-6x10
10
-8x10

0.2
0.0
0

1.0

-5000

0.8

-10000-150000.6-200000.4-25000

0.2

-30

-20

-10
0
10
time (fs)20

field strength (V/m)

5x10

EUV intensity (a.u.)2

intensity (W/cm )(a) 6x10

14

0.0
30

Figure 1.10: Dynamic phase-matching effects in EUV generation (parameters similar tosection 3.9). (a) intensity envelope of a 13 fs fundamental pulse. (b) electric field (blue)
and ionization fraction of the Argon gas (red). (c) phase mismatch for the 25th harmonicin 10 torr of Argon (red), summed-up intensity of 19th − 31st harmonic from 25 mm
of Argon gas, calculated with the simple model (1.14), with the additional constraintthat only fundamental intensities above the cutoff (1.8) contribute to each harmonic.
EUV emission does not peak at the fundamental intensity maximum but earlier: At
late times >∼ −5 fs EUV emission is suppressed by the large phase mismatch due tofull ionization of the gas, while at early times it is constrained by the low fundamental
intensity.

24
matching window, facilitating the generation of a single phase-matched attosecond pulse.
Such a constant offset can be introduced by quasiphasematching techniques, as wasshown in our group [116]. This technique was however not pursued in this thesis.

1.5

Temporal Characterization of ultrafast EUV radiation
Not only the generation, but also the temporal characterization of ultrafast EUV

radiation is an active field of research: In contrast to femtosecond NIR pulses, where
nonlinear effects are easily exploited to generate an autocorrelation signal, EUV fluxes
are low, and nonlinear experiments are difficult. However temporal characterizationof short events can as well be achieved by a cross-correlation with another event. The
most common method for characterization of EUV pulses is therefore a cross correlation
with the electric field of a strong NIR pulse, based on ”Laser Assisted Photoelectron
Emission”. Here EUV radiation and fundamental field are focused into a gas target withan adjustable delay. The EUV pulse causes photoionization, where the photoelectron
wave packet can be viewed as a replica of the EUV pulse. The photoelectron willthen receive a momentum shift (or, as we will see in section 3.4, a phase shift) by thefundamental laser field. The final photoelectron wave packet contains information on
both amplitude and phase of the EUV pulse, allowing a complete reconstruction of its
temporal structure.
When this cross-correlation signal is energy-resolved, a spectrogram results
¯Z +∞
¯2
¯
¯
¯
S(ω, τ ) = ¯E(t)g(t − τ ) exp (−iωt)dt¯¯(1.15)−∞

where E(t) is the electric field of the pulse to be measured and g(t − τ ) is the gatefunction. The most common FROG technique for the characterization of NIR laser
pulses, uses an amplitude gate. In contrast, laser assisted photoemission employs aphase gate g(t − τ ) = exp(iφ(t − τ )) where the NIR pulse causes a phase-modulation of
the photoelectron wave packet. Laser assisted photoemission, as well as our analysis of

25
the recorded spectrograms are described in detail in Chapter 3.

1.6

Applications of femtosecond / attosecond pulses

1.6.1

Molecular physics

Femtosecond EUV radiation is ideally suitable to initiate or probe molecular dynamics by ionization. Figure 1.11 shows a molecular potential diagram and gives an
overview of the energetics of EUV (energy hν) photoionization (green) AB + hν →AB + + e− of the photoexcited complex and photodissociation (red) AB + hν →AB +∗ + e− → A+ + B + e− + KER, where KER is the total kinetic energy release after subtracting the internal energy of the A and B products. Of course, eventhe simplest diatomic molecules can have very congested energy diagrams with several potential energy curves possibly crossing each other and leading to the same final
products. Time-resolved EUV-NIR pump-probe experiments with sufficient spectral
resolution have shown great potential to initiate and probe nuclear motions, or correlated electron-nuclear motions. EUV radiation is particularly suitable for excitation tohighly excited molecular states, which have been rarely studied in detail so far, boththeoretically and experimentally.

1.6.2

Condensed matter systems

Just as in molecular systems, EUV radiation may initiate photoionization orAuger processes in condensed matter systems, such as surface-adsorbate systems. A
proof-of principle experiment to observe such Auger decays in the time-domain wasrecently conducted in our group on noble gas atoms physisorbed on platinum [105].
From a time-delay between laser-assisted photoemission and laser-assisted Auger decay
signals, a lifetime of 7 fs of the 4d−1 core level of Xenon on Pt(111) could be determined.
Not only Auger decays, but also excited-state lifetimes and charge transfer timescales

26

E hν
Ekin,e(AB+)*

Ekin,eA+ + B

KER

AB+
Eint,AB+
IEr
AB
Figure 1.11: Basic energetics of EUV (energy hν) photoionization (green) and photodissociation (red) of molecules. Shaded area: Franck Condon region in which photoabsorption takes place.

of molecules chemisorbed onto a surface are expected to occur on femtosecond- or evensub-femtosecond timescales.

1.6.3

Strong-field physics

When an external electric field of comparable strength is superimposed on a nuclear field, there is a high probability for single or multiple ionization. An example isthe study of double ionization of noble gas atoms leading to correlated electron emission [170]. The data showed electron-electron correlations for double ionization at low
intensities, while supporting the picture of sequential ionization with no directional correlation of the electrons at high intensities. In the low intensity regime the data suggestthat first one electron is ionized, accelerated by the field, and is then driven back to its
parent ion where it transfers energy to eject the second electron.

27
A strong laser field can of course be applied to molecular systems as well. The
mechanism of strong-field electron tunneling, acceleration and recollision with the parent ion, can now be used to induce electron diffraction from the molecule [103]. The
high achievable return kinetic energies correspond to electron de Broglie wavelengths of∼ 1 Angstrom. One can therefore make use of the wave-nature of the returning electron
wave packet to obtain information about the parent molecule. In addition to the elastically scattered electrons which reveal information on the positions of the nuclei in themolecule, the momentum distribution of electrons moving directly, without scatteringto the detector reveals the symmetry of the highest occupied molecular orbital.
Another way to extract molecular information is a detailed analysis of the strengthof EUV generation from molecules [95]. This technique was recently shown to yield
dynamical information on coupled electronic-nuclear motions of polyatomic molecules[95]. Vibrations in N2 O4 were excited and stronger high harmonic emission was observedat the outer turning point of the dimer, when tunneling to the ground state of theion occurred, whereas weaker high harmonic radiation was observed when tunnelingoccurred to the first excited state of the ion at the inner turning point. Calculations
supported the experimental findings and explained them by a larger recombination
dipole (better electronic overlap) for high harmonic generation involving the groundstate of the ion.
As pointed out in the last example, strong-field physics is not limited to electron
motion alone. Strong-field ionization of molecules can start correlated electron-nuclear
motions (when the equilibrium configuration of the ion is different from the neutral
molecule). In a second step, electron recollision can lead to dissociation of the parent
molecular ion, and thus act as a probe of the nuclear motion [111]. What is evenmore exciting is that the laser field can continue to act on the dissociating molecule,controlling the carrier-envelope sensitive localization of the remaining electron on oneof the two dissociation products [85].

28

1.7

The COLTRIMS reaction microscope
COLTRIMS (COLd Target Recoil Ion Momentum Spectroscopy) [34] is a tech-nique which has the capability of detecting in coincidence all charged particles emerging
from a single reaction event. It also allows the reconstruction of the full 3D momentumof all particles. This technique has recently become very popular among the ultrafast
community, beginning with strong-field experiments described above.

1.7.1

Opportunities of fs-EUV pulses combined with COLTRIMS detection

The combination of ultrafast EUV pulses with the COLTRIMS technique provides a powerful experimental tool, which allows one to extract a maximum amount of
information from every event.
Applications include time-resolved studies combined with the capability of multiple coincidence detection. Such experiments have just begun to shed light on basic
processes in highly excited molecules, such as autoionization [139].
The coincidence detection of ions and electrons also allows experiments with
fixed-in-space gas-phase molecules: When simple molecules dissociate, the fragment
ion momenta point along the molecular axis at the time of dissociation. COLTRIMS
can measure such 3D momenta, and in addition measure momenta of electrons in coincidence with the ions. A major application of this technique is the measurement ofmolecular-frame photoelectron angular distributions. Such photoelectron angular distributions can be very complex and reveal detailed information e.g. about correlated
electron dynamics in molecules [30]. One new approach for measuring molecular-frame
photoelectron angular distributions in the case of nondissociating channels is describedin this thesis.

29

1.8

Organization of this thesis
This thesis is organized as follows: Chapter 2 describes the realization of a high-power fs pulse train which had its electric field stabilized underneath the intensity
envelope. In Chapter 3 of this thesis I will tell you about the generation and temporalcharacterization of extremely short EUV pulses: these pulses are shorter than one optical
cycle of the driving radiation, yet they are spectrally narrow enough to do state-selective
excitation in a condensed matter or molecular system. In the third part of the thesis,
Chapter 4, I will tell you about one application experiment, which allowed us to measure
the orientation of transition dipoles in small molecules.

Chapter 2
A carrier-envelope phase (CEP) stabilized amplifierThis chapter on the carrier-envelope phase stabilization of a femtosecond amplifiersystem contains material published in [157] and [50]. This project builds on my priorwork at NIST in Leo Hollberg’s group [158, 153, 28, 9] on the CEP stabilization ofa Chromium Forsterite femtosecond oscillator, which allowed the extension of phasestabilized frequency combs for absolute optical frequency measurements further into theinfrared region (∼ 1.1 µm to ∼ 2.2 µm) relevant for telecommunications and infraredmolecular spectroscopy.
During the course of this work I also participated in work in Jun Ye’s groupin which novel stabilization techniques of a femtosecond Ti:Sapphire oscillator to areference cavity were explored [78]. In particular, it was explored how to lock the twodegrees of freedom of the femtosecond frequency comb, f0 and fr , to the mode combof the cavity. In particular the limitations due to the residual dispersion of the cavity
were explored.

2.1

Introduction, Motivation and Difficulties

2.1.1

Motivation

The carrier-envelope phase (CEP) is defined as the phase difference between the
carrier oscillations and the pulse envelope of ultrashort laser pulses. Its definition andrelevance were shown in the introduction in Figure 1.2. In conventional femtosecond

31
laser oscillators this phase fluctuates randomly from pulse to pulse. After the first
demonstration of CEP stabilization of low-power femtosecond pulse trains in 2000 [76]this technique spread rapidly, driven by the huge interest in absolute frequency measurements and optical waveform synthesis, but remained restricted to low-power pulses.
The amplification of carrier-envelope phase stabilized femtosecond (fs) laser pulses has
only recently received considerable interest. One major driving force for this interest isthat extreme nonlinear processes such as HHG driven by amplified laser pulses, exhibit
a strong dependence on the driving laser field [11, 10, 22, 21], and are therefore sensitive
to the CEP of the driving laser pulses [38, 118, 7].
Combination of pulse shaping techniques [178, 177] with methods of CEP control,[76, 29] offers the possibility of controlling the complete electric field of the ultrafast
pulse in the time-domain, with attosecond precision. This allows us to access the fastest
time-scales to date that are accessible with modern laser technology. It has thus become
possible to manipulate electron dynamics with attosecond precision [11, 10, 21], tomanipulate phase-matching of the HHG process,[23, 116] and to generate pulses of lightwith sub-femtosecond duration [84, 152].
Interesting applications of CEP stabilization can be expected in molecular physics
and condensed matter systems. Using CEP control, it was e.g. possible to control electron localization in the dissociative ionization D2 → D+ + D [85]: CEP sensitive lightdriven intramolecular electronic motion before dissociation decides on which nucleus theelectron localizes. In solid-state systems, CEP stabilization allows the control of directional currents [4, 132], providing interesting perspectives for future ”opto-electronics”
technologies.

2.1.2

Where do CEP fluctuations come from?

To understand why there are shot-to-shot fluctuations of the carrier-envelope
phase in a femtosecond pulse train from an oscillator [62, 151], recall that a pulse

32
envelope travels at the group velocity vg = c/ng while the carrier oscillations travelat the phase velocity vp = c/n. These velocities are different inside a laser cavity due
to dispersive elements such as prisms, the laser gain medium, mirrors, and the beam
path in air. A round trip of length L of a carrier oscillation therefore takes a time
RL
RL
τp = 0 dz1/vp (z) while the pulse envelope takes τg = 0 dz1/vg (z). The phase shiftdifference between the carrier and the envelope for one round trip is
Z L∆φGP O = ω(τp − τg ) =

dz
0

2π
(ng − n)
λ

(2.1)

∂n
where (ng − n) can also be expressed as (ng − n) = ω ∂ω
, i.e. it depends onthe dispersive properties in the laser cavity. This phase difference between subsequent
pulses can be many full cycles. The measurable CEP difference between adjacent pulses
is only the sub-cycle part of this large phase slip

∆φCE = ∆φGP O mod 2π(2.2)

The carrier envelope offset frequency is defined as the rate of change of the CEphase:
f0 =1 dφCE
2π dt

(2.3)

Equation (2.1) shows that f0 is constant as long as dispersive beam paths in
the cavity remain constant. The CE offset can only be measured at time intervals
dt = 1/frep , so that we can also express f0 as

f0 =

∆φCE
· frep2π(2.4)

This shows that once the ratio of the two radio-frequencies f0 /frep is stabilized,
one has also stabilized the CE-phase slip in the optical domain.
In practice, there are several sources of CEP noise: All laser parameters thatare coupled to the intracavity dispersion contribute. As soon as e.g. beam pointing

33
variations, air pressure fluctuations, pump laser intensity fluctuations occur, the carrierenvelope offset frequency fluctuates. Temperature variations cause long-term drifts.
Through the nonlinear index of the gain crystal, the CEP also depends on intra-cavity
pulse energy fluctuations [67]. An important contribution to this effect arises from pumplaser noise [173].

2.1.3

History and methods of CEP stabilization

There are several ways to measure and/or stabilize the pulse-to-pulse CEP slip.
Jones et.

al.

[76] first demonstrated the carrier-envelope phase stabilization of a

Ti:sapphire laser in 2000 employing a method based on frequency domain measurements. This f-2f interferometer is the most widely used method to date to stabilize the
CEP slip, and has led to tremendous progress in the field of optical frequency measurements as now a single laser can be used to measure many absolute optical frequencies. It
should be emphasized however that this technique does not measure the absolute valueof the CEP but only its pulse-to-pulse slip, and additional measurements are required
if one wants to fix this absolute value.
The basic idea behind the f-2f nonlinear interferometer (described in more detailbelow, see Figure 2.1) is this: Produce an octave-spanning, phase-coherent frequency
comb. Pass the ”red” portion of the comb through a nonlinear crystal, where thesemodes are phase-coherently up-converted to ”green”, and combine the original green
and doubled red light on a fast photodiode. The original green modes of the frequency
comb evolve in time as exp(i2π(mfrep + f0 )t) while the doubled red modes evolve as
exp(i2π(2nfrep + 2f0 )t), so the interference signal on the photodiode has componentscos(2π((2n − m)frep + f0 )t). This allows us to measure the beat frequency f0 .
There are two ways to produce a coherent octave-spanning frequency comb: Either a standard Ti:Sapphire laser is used in conjunction with a microstructure fiber
as in [76], or the generation of an octave spanning spectrum directly from a modified

34
Ti:sapphire oscillator [45]. Alternatively, one may use a modified laser [125] in combination with a 2f-3f interferometer, or use difference frequency generation in a PPLN
crystal [126]. In addition, new methods are being explored that do not rely on a f-2f
interferometer, such as the stabilization of both degrees of freedom of a femtosecond
laser to a reference cavity [78].
To actuate on f0 one can either use feedback on an AOM controlling the pumplaser intensity, or use a piezo-actuated tip-tilt mirror in the arm of the laser cavity where
the spectrum is dispersed. The AOM method achieves higher bandwidths (150 kHz),
while the tip-tilt mirror (tens of kHz bandwidth) avoids the laser intensity fluctuations
associated with the AOM method [29].
Of course there are also methods of stabilizing the CEP which employ processes
that are directly sensitive to the absolute position of the peaks of the electric field intime domain, such as photoionization with ultrashort pulses. Paulus et al. [118, 119]
measured CEP dependent effects in above-threshold ionization (ATI) using a stereoATI setup. Here, an ultrashort pulse causes multi-photon above-threshold ionization ofa gas target, whereby photoelectrons are preferentially ejected in the direction of thestrongest optical half-cycle of the pulse. By measuring the difference in photoelectron
yield with two identical detectors placed on opposite sides of the gas target one canmeasure the absolute CEP.
In a similar way as ATI from a gaseous sample, also photoelectron emission frommetals using few-cycle pulses was predicted to be CEP sensitive (Lemell et al. [91]).
This effect was later experimentally measured by Apolonski et al. [4].
Roos et al. [132] used interferences between one- and two-photon transitions in asemiconductor to induce a current with a CEP-dependent sign and magnitude that wasused to stabilize the CEP. While this experiment still required a microstructure fiber tobroaden the spectrum to an octave, with octave spanning lasers and improved signal tonoise this method could become an alternative stabilization scheme based entirely on

35
solid-state systems. Similar effects were seen by Mücke et al.[108].
Another highly CEP sensitive process is high-harmonic generation. Durfee et al.
observed possible signatures of the CEP in fluctuations of the yield of high-harmonic
generation from CEP-unstabilized pulses [71]. Carrier-envelope dependence in the generation of attosecond pulses was reported in [7].

2.1.4

CEP concerns with amplified pulses

The amplification of CEP stabilized pulses through chirped pulse amplification(CPA) [148] poses further challenges. There are two major concerns: First, pulse stretching before amplification and recompression afterwards require the use of strongly dispersive elements. In our setup, this is achieved by a grating-based stretcher and compressor[161]. The first CEP stabilized amplifier had been demonstrated with a material-based
stretcher and compressor [7]. Grating-based systems were suspected to be very susceptible to introducing CEP noise [62]. The basic reason is that a beam pointing fluctuation
changing the beam position on a grating by just one groove introduces a 2π CEP change[62]. The second concern is CEP changes caused by fluctuations of the nonlinear refractive index in the amplifier gain medium. However such fluctuations are not expected tobe very strong, as amplifiers are designed to have a total accumulated nonlinear phase(B-integral) less than 2π. The relevant quantity is again the dispersion of the nonlinear− 17 cm2 /W
2refractive index of the Ti:Sapphire gain medium (ng − n) = ω ∂n
∂ω = 8 · 10[62] in equation (2.1). In [62] it is found that about 6% intensity fluctuations should be
tolerable for a CEP noise below 100 mrad.
As pointed out above, intensity fluctuations which cause phase changes due tononlinear refractive index changes might not strongly contribute to CEP changes. Nevertheless cryo-cooling of the amplifier crystal [5] is important to significantly reducebeam pointing fluctuations (leading to large changes in beam path through the amplifier crystal, lenses or beam pointing fluctuations onto the compressor gratings). These

36
effects can be diminished by cryo-cooling. Usually the heat load due to the pumplaser creates very strong temperature gradients. Due to the dependence of the sapphire refractive index on temperature this causes thermal-lens aberrations. By coolingthe crystal to liquid nitrogen temperatures (77 K), the thermal conductivity increases
and the change in index of refraction with temperature decreases, reducing thermal
distortions by a factor of 200. Therefore it likely reduces beam pointing effects due tointensity fluctuations from the amplified pulses or pump pulses and therefore decreases
CEP noise.
In the following sections I will describe our procedure to demonstrate a CEP stabilized amplifier. First, a microstructure fiber was used to generate an octave spanningspectrum from a portion of the oscillator output, and an f-2f interferometer was used todetect the offset frequency and thereby stabilize the oscillator’s carrier-envelope phase.
As our next step towards setting up a CEP stabilized amplifier, we analyzed the behavior of a grating-based stretcher and compressor (SC) setup. Our work, as well as theresults of Kakehata et al. [80], showed that grating-based chirped pulse amplifiers canbe stabilized. This work therefore proved that it will be possible to stabilize amplifierswith pulse energies up to several mJ or even into the Joule range [68]. It turned outthat stabilization of the oscillator CEP, in combination with the intrinsic CEP stabilityof a cryogenically cooled amplifier, is sufficient for a rough CEP stabilization of the full
amplifier system. After the amplifier at most a slow feedback is required for correcting
low frequency noise.

2.2

A CEP stabilized oscillator
In this work, a prism-based oscillator was CEP phase stabilized to serve as theseed oscillator for an amplifier. The CEP slip given by equation (2.4) was measured
and locked using a f-2f fiber setup, shown in Figure 2.1. The spectrum of the oscillator
was broadened to more than an octave, using self-phase modulation in a ∼ 5 cm long37
microstructure fiber (Crystal Fibre). Typically about ∼ 150 mW were used and the fiber
coupling efficiency was ∼ 35 % (Newport microscope objective with numerical aperture
0.65 and 0.85). Infrared and green colors are split using a double pass through a prism
pair with a split end mirror. The infrared pulse is then frequency-doubled in a LBO
crystal, and is spatially and temporally overlapped on a photodiode with the original
green pulse. As described above, this results in a measurement of the beat frequency
f0 .

Prism-basedfs oscillator

Microstructure
Fiber

CEP
Control(tip/tilt PZT)

Delay line
frep

Phase Locked Loop
Electronics

Infrared

VisibleLBO

f0

FilterFigure 2.1: Sketch of the f-2f interferometer used to lock the CEP of the amplifier
seed oscillator [76, 29]: self-phase modulation in the microstructure fiber broadens theoscillator output to an octave. Infrared and green colors are split and sent through a
LBO crystal which causes sum-frequency generation of the near-infrared modes to green.
The two green beams are overlapped on a photodiode where their interference producesa radio-frequency beat signal at the carrier-envelope offset frequency f0 . One of the
split mirrors at the end of the prism sequence is mounted on a delay stage to optimize
the temporal overlap of the two green fields on the photodiode. The prisms are used
for dispersion compensation to optimize doubling efficiency of the IR pulse. The laser
pulse repetition rate frep is also recorded. Both signals are fed into the phase-locked
loop electronics, which generates a voltage signal for feedback to a tip/tilt PZT mirror
inside the laser cavity to lock the ratio f0 /frep , and hence ∆φCE according to equation(2.4).

38
Note that different interferometer configurations have been used for oscillator
CEP stabilization. The setup of Ref [44] employs an AOM in one interferometer arm.
This allows one to shift f0 to zero (generating a train of identical pulses), but stilldetect it at the nonzero AOM frequency. In contrast, our setup does not easily allow
shifting f0 to zero, but this is not required for our application (see below). The geometry
involving a prism pair with a split end mirror was chosen as it introduces less losses
than a Mach-Zehnder interferometer and therefore allows for higher signal to noise beatnote detection.
The electronics which is used to process this beat signal is sketched in Figure 2.2.
The purpose is to lock f0 to a pre-set fraction (here 3/8) of frep using a phase detector
and loop filter. The digital phase/frequency detector provides a voltage proportional
to the phase difference of the two input signals. The loop filter provides sufficient gain
to drive fluctuations of the phase difference to zero. The error signal is sent to a piezoactuated tilt mirror in the frequency dispersed arm of the oscillator. The bandwidth of
this servo loop is approximately 10 kHz (limited by the PZT mirror).
Results for the locked CEP are shown in Figure 2.3. (a) shows the RF spectrum
recorded with the ”f0 ” photodiode, extending from DC to 100 MHz. The pulse repetition rate is visible at frep = 96 MHz. The phase-locked beat note f0 is visible at 36
MHz. The peak at 60 MHz corresponds to frep − f0 . (b-d) show successively zoomed-in
spectra of the beat note at 36 MHz, exhibiting various residual noise features. (e) shows
the in-loop CEP noise at frequencies > f0 on a logarithmic scale. The decrease of noisewith decreasing frequency below 10 kHz clearly shows that the lock efficiently cancels
noise frequencies < 10 kHz.
The rms in-loop phase fluctuations for this stabilized oscillator are shown in Figure
2.4, measured with a FFT spectrum analyzer that allows a smaller resolution bandwidththan in the measurements of Figure 2.3. To make this measurement, an electronic
reference signal at 3/8 frep was generated in order to mix f0 to DC. The phase noise

39
f0
TBP
Spectrum
analyzer+48dB
70 MHzLP (2x)frep/Nrep

frep
+24dB

Phase
Locked Loop
Electronics
mirror

f0/N0

φ-det
fs synchronizer
Loop filter
Comb servo
V0+∆V

V0-∆V

PZT’s

Figure 2.2: Phase-locked loop electronics used to stabilize the CEP slip of the oscillator[29]. f0 and frep are recorded as shown in Figure 2.1. f0 is sent through a tunablebandpass filter (TBP), amplified and sent through two low-pass filters (LP). frep is also
amplified and filtered. Both frequencies are electronically divided by suitable integers(N0 and Nrep , respectively) and compared on a phase detector. Its voltage output,
proportional to the phase- (or frequency-) difference serves as the error signal. This issent to a loop filter, which provides proportional and integral gain, as well as additional
low-pass filtering for the error signal. The ”comb servo” provides suitable high-voltage
signals to drive a piezoelectric tilt-mirror. For our experiments, N0 and Nrep are chosen
to yield f0 /frep = 3/8.

accumulates to ∆φCE ∼ 300 milliradians over 16 seconds (integrated from 63 mHz to 102
kHz). Typical values achieved on a daily basis (as presented in the stretcher/compressor
measurements in section 2.3) were ∆φCE ∼ 400 milliradians.
In practice, for a successful lock, a good signal-to-noise beat note needs to beachieved. Environmental noise needs to be kept at a minimum to obtain a good passive
stabilization, before active stabilization is attempted. Noise sources should be identified
and removed so that the loop only has to deal with the remaining noise. As the beat(a) -40

Trace007from -5 to 100MHz, Rbw 1kHz
DC

signal (dBm)

-60

frep

(b) -60

Trace003
span 100kHz,
Rbw 10Hz-70

Locked beatsignal (dBm)

-50
-70
-80
-90

-80
-90
-100
-110

-100
-110

40

-50

-120

0

7

2x10

7

7

7

4x10 6x10 8x10
frequency (Hz)

8

1x10

-50

(c)

4
4
4
4
0
-4x10 -2x10
2x10 4x10
frequency - 36110454 (Hz)Trace002
span 10kHz,
Rbw 10Hz

signal (dBm)

-60

-50

signal (dBm)

2.55kHz1.69kHz-6000 -4000 -2000 0 2000 4000 6000
-50
frequency - 36110454 (Hz)

(d)

-60

-110
-120
1

1.16kHz

-120

-80

-100

950Hz

-90

-110

-70
-90

420Hz

-80

-100

RBW 10Hz

10
100 1000 10000100000
frequency - 36110454 (Hz)signal (dBm)(e)-60-70-70

f0 = 36110454 Hz

Trace001
span 1kHz,
RBW 10Hz

-80
-90

-100
-110
-120
-600 -400 -200 0
200 400
frequency - 36110454 (Hz)600

Figure 2.3: Measurement of f0 . (a) shows the RF spectrum recorded with the ”f0 ”
photodiode. (b)-(d) Zooming in on the CEP beat signal. (e) In-loop noise on a logscale representation at frequencies > f0 . The feature below 10 Hz corresponds to theresolution bandwidth limited coherent spike, i.e. it is not a measure of true noise.

note is a very delicate signal, all beam paths should be air tight to avoid air pressure
fluctuations - particularly at dispersive elements. Acoustically isolating enclosure boxes
for the beam path as well as for noisy equipment are necessary. All elements in the
beam path should be mechanically stable (i.e. low and thick mounts). A stable labtemperature is essential, especially at the delicate microstructure fiber. Vibrations from

41

1

1E-3

1E-5

2

0.1

PSD (rad /Hz)∆φCE (rad)

1E-4

1E-6
1E-7

0.01

1E-8
1E-3 -2
10

10

-1

0

10

1

2

10
10
10
frequency (Hz)

3

10

4

10

1E-9

5

Figure 2.4: Measurement of in-loop oscillator CEP noise using a FFT spectrum analyzer.
Red, phase noise power spectral density (radians2 /Hz). Black, accumulated root meansquare (rms) phase fluctuations ∆φCE .

water lines, vacuum pumps, etc need to be damped and isolated. Any noise transmitted
to the table needs to be eliminated (floating of the table is one consideration). Anothernoise source are fans, which can produce physical vibrations, air pressure variations andalso electrical noise. Electrical noise sources and ground loops are additional major
concerns. Before any equipment was moved into the lab, the room noise and floor
vibrations were evaluated by accelerometer measurements.
The work described in this section provides the groundwork for the measurementsin the next sections, as well as for the CEP stabilization of a complete amplifier setup.

42

2.3

Investigation of a grating-based stretcher/compressor for carrierenvelope phase stabilized femtosecond pulses
In this chapter, we experimentally investigate the effect of a grating based pulse

stretcher/compressor on the carrier-envelope phase stability of femtosecond pulses. Grating based stretcher-compressor (SC) setups have been avoided in past demonstrations[7] of chirped pulse amplification (CPA) of carrier envelope phase (CEP) stabilized femtosecond pulses, because they were expected to introduce significantly stronger CEP
fluctuations than material-based SC systems [62, 162]. The CEP change in a double
pass through a grating compressor is [162]∆φCE = 4π

Gtan(γ − θ(ω0 ))
d

(2.5)

where G is the perpendicular grating distance, d is the groove period, γ is theangle of incidence, and θ(ω0 ) is the angle between input beam and the diffracted ray ofthe center frequency. If the path through the compressor is identical for different pulses,
their CEP change is identical. However input beam fluctuations ∆γ lead to pulse-toG
6−6 rad,pulse CEP flucutuations of order 4π G
d ∆γ. Typically d ∼ 10 and ∆γ . 10

making it conceivable that eq. 2.5 could be significant. It turns out that cancellations
between the first and second pass reduce the fluctuations somewhat, allowing gratingbased optics to be used for CEP stabilization.
Using a microstructure fiber-based detection setup, we measure CEP fluctuationsof ∆ΦCE,SC = 340 milliradians rms for a frequency range from 63 mHz to 102 kHz for
pulses propagating through the SC setup. When bypassing the beam path through theSC, we find CEP fluctuations of ∆ΦCE,bypass = 250 milliradians rms. These values contain significant contributions from amplitude-to-phase conversion in our microstructure
fiber-based detection setup for ∆ΦCE . Hence, we do not unambiguously measure any
added CEP noise intrinsic to the SC setup. To distinguish between intrinsic SC effects

43
and amplitude-to-phase conversion, we introduce controlled beam pointing fluctuations∆α and again compare the phase noise introduced when passing through / bypassing the
SC. Our measurements do not reveal any intrinsic effects of the SC system, but allow us
to place an upper limit on the sensitivity of our SC system of ∆ΦCEintrinsic,SC < 13000
rad/rad. Our results demonstrate experimentally that there is not a strong couplingmechanism between CEP and beam pointing through a stretcher/compressor , as wellas measuring significantly smaller CEP fluctuations than experimental results reported
previously.

2.3.1

Introduction

Chirped pulse amplification (CPA)[148] is the most widespread technique for amplification of fs pulses. In this scheme the pulse is stretched before amplification byintroducing a positive chirp, and afterwards recompressed by compensating for the positive chirp introduced in the stretcher and gain material with an equally large negative
chirp. Amplified CEP stabilized pulses were first produced using stretchers based onmaterial dispersion followed by compression by prism compressors [7]. These systems
reach pulse energies of ∼ 3 millijoules, limited by the required amount of stretching andrecompression [144].
These limitations could be overcome by CPA using grating based stretcher /compressor systems. Such systems however, have been predicted to have a more severe
effect on CEP stability than material-based stretcher compressor systems, due to astronger coupling of beam pointing fluctuations to CEP fluctuations [62].
In this work, we quantitatively investigate the effect of a grating based stretcher
compressor setup on CEP stability. We employ two self-referencing setups [29] todetect the root mean square (rms) CEP fluctuations both in the oscillator stabiliza0tion loop ( ∆ΦCE ) and out of loop (∆ΦCE ), as shown in Fig. 2.5. The difference0∆ΦCE,SC := ∆ΦCE − ∆ΦCE is a direct measure of CEP fluctuations introduced outside

44

Figure 2.5: The setup consists of a prism-based fs laser coupled into a grating-based
stretcher-compressor (SC). Two microstructure-based setups measure the offset frequency of the phase-locked laser spectra, after the oscillator (in-loop, f0 ) and after
the SC (out of loop, f00 ). These are converted into phase fluctuations using Eq. 2.6.
The difference between CEP fluctuations introduced inside and outside the oscillator
stabilization loop are measured by mixing f0 − f00 , and FFT analyzed. Optionally thebeam bypasses the SC. A swivel mirror before the SC allows introduction of controlled
beam pointing fluctuations.

the oscillator stabilization loop, in the beam path through the stretcher-compressor. We
perform the measurement both with pulses that have passed the SC setup (∆ΦCE,SC ),as well as with pulses that bypass the stretcher compressor (∆ΦCE,bypass ). Our results,
presented below, show quantitatively that the coupling between beam pointing and CEP
introduced in our grating based SC setup is sufficiently small to enable phase stabilized
amplification using a standard stretcher / compressor CPA system.
This work adds to recent results reported by Kakehata et al.[80] that show CEP
stability of oscillator pulses can be retained after amplification to 3.5 mJ using a regenerative plus multipass amplifier system, together with a grating-based stretchercompressor. Their measurement of CEP changes introduced by beam pointing fluctuations did not separate the effects of CEP fluctuations in the stretcher and compressor

45
from additional CEP fluctuations in the regenerative amplifier and amplifier ring, as
well as amplitude-to-phase conversion in the CEP detection setup (using a Krypton gas
filled hollow fiber for spectral broadening). Furthermore, in that work it is difficult todistinguish between CEP changes and pulse timing fluctuations, due to the spectralinterferometry technique that was used over a limited wavelength range.
Our measurements are based on a different CEP detection method that does not
introduce an ambiguity between CEP changes and timing fluctuations. We also take
into account amplitude-to-phase conversion in our CEP detection setup by comparing
measurements of pulses propagating through, as well as bypassing, the SC setup. Our
measurements therefore extend and clarify the results of Ref. [80]. Finally, we demonstrate experimentally that there is not a strong coupling mechanism between CEP andbeam pointing through a stretcher/compressor, as well as measuring significantly smaller
CEP fluctuations than experimental results reported previously.
2.3.2

Setup and measurement methods

Our setup is shown in Fig. 2.5. It consists of a CEP stabilized prism-based
Ti:Sapphire oscillator producing pulses of ∼ 25 fs duration, with a repetition rate offrep = 96 MHz and a spectrum centered at 820 nm, with an average power of 850
mW. For CEP detection we use a self referencing setup using a 4.5 cm long air-silica
microstructure fiber to broaden the spectrum to an octave. This setup allows direct
measurement of the offset frequency f0 of the modelocked spectrum. The offset frequency f0 is related to the pulse-to-pulse CEP slip ∆ΦCE by

f0
∆ΦCE
=
frep
2π
The repetition rate frep is detected on a separate photodiode.

(2.6)
We stabilize

f0 /frep = p/q to 3/8. The ratio p/q = 3/8 ensures that every 8th pulse experiences
a 3 · 2π phase slip and is therefore indistinguishable from the 1st pulse. Practically,

46
CEP stabilization is achieved using a piezoelectric tilt mirror, achieving a loop bandwidth around 10 kHz. The measured rms in-loop phase fluctuations are 400 milliradians(integrated from 63 mHz to 102 kHz).
Pulses from this oscillator are then sent through a grating based stretcher in a
double pass configuration. It consists of a grating (1200 grooves/mm) and a curved
imaging mirror of 406 mm focal length. The stretched pulse duration, at 220 picoseconds, is suitable for amplification up to Joule or higher pulse energy level [169]. Pulse
recompression to ∼ 35 fs is achieved using a 1200 grooves/mm grating pair in double
pass configuration.
Measurement of the offset frequency f00 of the recompressed pulses is performed
using a second self-referencing setup similar to the first one. From the measurement0

of f00 , the phase noise ∆ΦCE is determined from Eq. 2.6. In order to measure thefluctuations of CEP introduced outside the oscillator stabilization loop, i.e., ∆ΦCE,SC :=0∆ΦCE − ∆ΦCE , we mix the f0 and f00 photodiode signals to an output signal around
DC. The mixer output voltage is Vmixer ∼ cos(∆ΦCE,SC + φ), where φ is an arbitrary
phase offset. For suitable φ and small ∆ΦCE,SC , Vmixer ∼ ∆ΦCE,SC is proportional
to the phase difference to be measured. We take care that the fluctuations ∆ΦCE,SC
are not larger than π/5 so that the mixer output is a true representation of the phasenoise ∆ΦCE,SC . The signal is analyzed on an FFT signal analyzer (62.5 mHz to 102.4
kHz range). For each frequency range we take an average over four data sets. The FFT
2 /Hz is converted to the CEP power spectral density (PSD) ∆Φ2
signal Vrms
CE,SC,rms /Hzusing the mixer output peak-to-peak voltage corresponding to ∆ΦCE,SC = π.
The phase noise ∆ΦCE,SC is obtained from the power spectral density by integrating from the upper frequency fu to the lower limit fl of the FFT frequency ranges Z∆ΦCE,SC =2

fl ∆Φ2
CE,SC,rms

fu

Hz

df

(2.7)

47
2.3.3

Results and discussion

Figure 2.6: Comparison of CEP fluctuations a) passing through the SC, b) bypassing
the SC. Red: power spectral density (PSD) ∆Φ2CE,SC,rms /Hz, Black: integrated CEPnoise given by Eq. 2.7

Figure 2.6 (a) shows the measured power spectral density of phase fluctuations,∆Φ2CE,SC,rms
Hz(red curve), as well as the RMS phase fluctuations ∆ΦCE,SC (black curve)

introduced when the pulses propagate through the stretcher compressor. The RMS
phase fluctuations ∆ΦCE,SC are obtained from the PSD using Eq. 2.7. Figure 2.6 (b)shows the corresponding data measured when the pulses bypass the stretcher compressor.

48
For pulses passing through the stretcher compressor, we measure ∆ΦCE,SC = 340
milliradians of CEP fluctuations, whereas we measure ∆ΦCE,bypass = 250 milliradiansfor pulses bypassing the stretcher-compressor. Both values are dominated by the effectsof mechanical resonances of optical components in the frequency range from 100 Hz to600 Hz.
We expect that the CEP fluctuations ∆ΦCE,bypass of the bypassed beam would bedominated by nonlinear amplitude-to-phase conversion in the detection setup for ∆Φ0CE[46, 173]. The slightly larger value of ∆ΦCE,SC = 340 millirad when passing through thestretcher-compressor, may either be caused by additional CEP fluctuations introduced
by stretcher-compressor, but may also be due to slight differences in alignment, locksettings or differing optical mounts and beam paths. The close similarity of the values∆ΦCE,SC and ∆ΦCE,bypass therefore does not permit a precise determination of effects
intrinsic to the stretcher-compressor. We have measured the RMS beam pointing fluctuations of the laser beam into the SC setup to be ∆αrms < 0.1 microradians, assuming
the beam fluctuations to originate from the oscillator Ti:sapphire crystal. We note that
this allows us to only set a relatively large upper bound of beam pointing sensitivityof the SC setup, ∆ΦCE,SC /∆αrms < 3.4 106 rad/rad, likely dominated by effects not
intrinsic to the SC.
In order to obtain a clearer signature of CEP effects occurring in the stretchercompressor setup, we artificially introduce a beam pointing oscillation of controlled
amplitude. We use a swivel mirror in front of the stretcher compressor, at a distance of
90 cm to the first grating. We again analyze the introduced phase fluctuations ∆ΦCE,SC
on a FFT signal analyzer. In this way we can separate the spectral component at theswivel frequency 50 Hz from all other CEP fluctuations.
As the beam pointing oscillations inevitably cause amplitude to phase coupling inthe second self-referencing setup, we have performed the measurement both for a beam
propagating through the SC, and for a beam bypassing it with a similar path length to49
the second microstructure fiber.

Figure 2.7: Measurements of carrier-envelope phase-fluctuations ∆ΦCE , power fluctuations ∆Prms and the ratio of both, when beam pointing fluctuations ∆α are
introduced.(a-c): data for stretcher-compressor, (d-f): data for bypassing beam.

Figure 2.7 shows the results of this measurement through the stretcher compressor. Fig. 2.7(a) shows the measured CE phase fluctuations ∆ΦCE,SC vs. the beam
pointing angle ∆α, defined as the peak-to-peak angle of beam deviations. The data
show a clear linear dependence with a slope of ∆ΦCE,SC /∆α = 3.9(±0.1) 104 rad/rad.
As we show, below this value is dominated by amplitude-to-phase coupling in the second self-referencing setup. The beam pointing angle is typically limited to ∆α ∼ 17
microradians in order to keep fluctuations ∆ΦCE smaller ∼ π/5. In Fig. 2.7(b) we√plot the simultaneously measured rms power fluctuations ∆Prms = ∆Ppp /(2 2),where50∆Ppp are the peak-to-peak power fluctuations detected after the second microstructured
fiber. Figure 2.7(c) shows ∆ΦCE,SC /∆Prms , where only the power fluctuations due toswiveling are used, i.e., the offset of the linear fit of ∆Prms vs. ∆α has been subtracted
from ∆Prms (this offset results from steady-state beam fluctuations not related to theartificially-induced swiveling). We obtain a value of ∆ΦCE,SC /∆Prms = 2170 ± 180
rad/W, where the error is the standard deviation of the data points.
The data bypassing the stretcher-compressor are shown in Figs. 2.7(d)-(f). Againa linear dependence of ∆Prms and ∆ΦCE,bypass on ∆α is seen, and again we take theratio ∆ΦCE,bypass /∆Prms . We expect this value to be equal to the amplitude-to-phaseconversion coefficient Cap, and obtain ∆ΦCE,bypass /∆Prms = 2130 ± 630rad/W , inapproximate agreement with Refs. [46, 173].
Comparing our data obtained by going through the SC and bypassing it, we seethat the ratio ∆ΦCE /∆Prms is identical in both measurements, and we conclude that
intrinsic fluctuations due to the SC are not contributing significantly to ∆ΦCE,SC . From
our data, we can place an upper limit on the intrinsic CE phase fluctuations introducedby the stretcher compressor ∆ΦCEintrinsic,SC /∆α < 13000rad/rad.
We obtain this value by taking the difference∆ΦCEintrinsic,SC /∆Prms = ∆ΦCE,SC /∆Prms − ∆ΦCE,bypass /∆Prms = 40 ± 660rad/W(2.8)
We convert to ∆ΦCEintrinsic,SC /∆α by writing∆ΦCEintrinsic,SC /∆α = ∆ΦCEintrinsic,SC /∆Prms · ∆Prms /∆α(2.9)

and take ∆Prms /∆α = 18.0(+/ − 0.7)W/rad from the slope in Fig. 2.7. This yields∆ΦCEintrinsic,SC /∆α = 740 ± 12000rad/rad, i.e. < 13000rad/rad.
Comparing this to [80] we find our upper limit for the intrinsic CE phase fluctuations introduced by the stretcher compressor to be 2.3 times smaller. The difference islikely due to amplitude-to-phase noise conversion in the hollow fiber and some ambiguity

51
due to contributions from delay changes in the spectral interferometry setup. Contributions due to the amplification process itself are common to all configurations of CPA
systems, and have proven to be sufficiently small as to not preclude CEP stabilization[7, 80].

2.3.4

Conclusions regarding grating-based stretcher compressor systems

We have carefully measured CEP fluctuations introduced by grating-based stretcher
compressor systems for amplifiers using a standard design of chirped pulse amplification.
From our error analysis, we find a very small upper limit on ∆ΦCEintrinsic,SC /∆α =13000rad/rad for our set-up. From our measured steady-state beam pointing fluctuations of ∆αrms < 0.1µrad, we would expect intrinsic CEP fluctuations ∆ΦCEintrinsic,SC <3.6 milliradians. Our results confirm and improve upon the conclusion of Kakehata [80]that grating based CPA systems are not a severely limiting factor for amplification ofhigh power CEP stabilized pulses. Since our measured noise is > 2× smaller than past
results, there is considerable future room for improvement. Finally, we also verified
experimentally for the first time that there is no severe coupling mechanism between
beam pointing in a stretcher/compressor and the CEP.

2.4

Long-term carrier-envelope phase stability from a gratingbased, chirped pulse amplifier
Having demonstrated that a grating-based stretcher and compressor do not intro-

duce significant obstacles to CEP stabilization, we now demonstrate a carrier-envelope
phase (CEP) stabilized, cryogenically cooled chirped pulse laser amplifier that exhibits
greatly improved intrinsic long-term CEP stability compared with that of other amplifiers. Single-shot carrier envelope phase noise measurements are also presented thatavoid underestimation of this parameter caused by fringe averaging and represent arigorously accurate upper limit on CEP noise.

52
2.4.1

Electronics for CEP stabilized amplifier

Here I briefly describe the electronics that provide a train of CEP-identical seedpulses to the amplifier. The setup is shown in Figure 2.8. The setting f0 /frep = 3/8
chosen in section 2.2 for the oscillator offset frequency means that the n’th pulse in
the oscillator train has a CEP slip of n · 2π · 3/8. In order to provide a train of CEPidentical pulses, the ”femtosecond synchronizer” was modified to provide an output
at frep /8 synchronized with CEP-identical oscillator pulses. This signal, instead of
the conventionally used frep signal is fed into the ”KM board” which picks a suitable
integer N and divides the input frequency down to the desired amplifier repetition rate
frep,amp = frep /(8N ) ∼ 1kHz. The output of the KM board is sent to a delay generator(Stanford research systems DG535) which triggers both the amplifier pump laser and
the Pockels cell that selects seed pulses for the amplifier. This setup ensures that only
identical pulses can be picked as seed pulses.

f0

frep

frep/Nrep

f0/N0

φ-det
fs synchronizer

frep/8Phase
Locked Loop
Electronics

to loop filter: lock f0 / frep = 3/8
KM board:N

frep,amp=
frep/8N

SRS
delay
generator

to pump laser
to pockels cell

Figure 2.8: Electronics that provide a train of CEP-identical seed pulses to the amplifier.
The fs synchronizer is modified to provide a signal at frep /8. This signal, which issynchronized with a subset of CEP-identical oscillator pulses, is divided down to provide
the amplifier repetition rate ∼ 1kHz, and is sent to the Pockels cell and amplifier pumplaser.

53
2.4.2

Measurements and results

Whereas the carrier-envelope phase (CEP) stabilization of femtosecond Ti:sapphireoscillators is now a well-established technology [76, 174, 77], stabilization of laser amplifiers is new, and the technology is still under development. The appeal of high-powerstabilized lasers is that they make possible many interesting strong field experiments[134, 31, 32]. Two designs have been demonstrated to date: Baltuska et al.[8] demonstrated a chirped pulse amplifier system[148] that uses material to stretch the pulse andprisms to compress it, while Kakehata et al.[80] showed preliminary work on a gratingbased chirped pulse amplifier system. In principle, grating-based amplifier systems canbe scaled to much higher output energies than can material- and prism-based systems;
therefore it is important to address questions regarding their long-term stability. In
previous work[157] in which only a laser oscillator was used, we showed that properlyaligned grating-based stretcher compressor pairs do not destroy CEP coherence.
In this work we demonstrate, for the first time to our knowledge, a CEP stabilized amplifier system that exhibits excellent intrinsic long-term coherence, i.e., withcoherence time scales of the order of tens of minutes. The shot-to-shot rms phase jitterof pulses from the system is 650 mrad in 0.5 s and appears to be limited primarily by
the oscillators CEP lock stability. The slow drift of the CEP can be tracked over longtime intervals > 30 min. These results represent an order-of-magnitude improvement
for long-term stability and shot-to-shot fluctuations over those reported previously for
grating-based amplifier systems. Moreover, the measurements presented here represent
to our knowledge the first true shot-to-shot reported characterization of carrier-envelope
offset phase from a chirped pulse amplifier system. Previous measurements of carrierenvelope offset from both grating- [80] and material-based [8] systems presented data
averaged over 16 30 shots, averaging out nearly all the actual CEP noise. In contrast, we
present single-shot measurements, which yield accurate high-frequency phase noise es-

54
timates while also demonstrating a long coherence time. This amplifier design presents
no barriers to scaling to much higher output energies. Finally, we note that the excellent long-term intrinsic CEP stability demonstrated here obviates the need for a slow
feedback on the amplifier system in many situations while avoiding noise that could
be introduced in additional feedback systems. Methods used for CEP detection werereported previously [127, 44, 79] and can be implemented by use of either the timeor the frequency-domain setups. Time-domain phase detection and stabilization, usedwith high repetition rate oscillators, are achieved by beating together two frequency
components of an octave-spanning laser pulse. One component is centered at 2f, while
the other is the second-harmonic signal of the component centered at f. The time delay
between the two beams is set to near zero, and the signal is detected by a photodiode.
The signal is22S(t) = Ef2 (t) + E2f(t) + 2[Ef2 (t)E2f(t)]1/2 cos[2φf (t) − φ2f (t) + φ0 ](2.10)

where φf (t) = n frep + f0 and φ0 is the absolute carrier-envelope phase. The offset
frequency, f0 , may then be determined fromf0 = ∆φ0 frep /(2π)(2.11)

where frep is the repetition frequency and ∆φ0 is the slip in CEP from shot to shot. If
the ratio of f0 to frep is locked, the pulse-to-pulse CEP slip is fixed.
In frequency-domain detection, which is appropriate for a lower repetition ratepulse train from a laser amplifier, a spectrometer is used to measure the phase byintroducing a time delay between the f and 2f beams. The signal is then given by2
2S̃(ω) = Ef2 (ω) + E2f(ω) + 2[Ẽf2 (ω)Ẽ2f(ω)]1/2 cos[2φ̃f (ω) − φ̃2f (ω) + φ0 ](2.12)

This signal produces an interference fringe pattern. Shifts in the fringe pattern mirror
changes in the CEP.

55
In our experiment, the front end of the laser system consists of a stabilized, prismbased laser oscillator incorporating a piezoactuator-controlled end mirror (see Fig. 2.9).
The oscillator output has an average power of approximately 750 mW at 98 MHz. Partof the oscillator beam is used to derive a signal to phase lock the oscillator. When the
CEP slip is locked, the out-of-loop rms CEP noise of our oscillator is ≈ 500 mrad for
16 s integration time, under conditions of minimal acoustic noise.
Most of the oscillator energy is used to seed the amplifier system. Timing forthe pump laser and a Pockels cell is derived from the offset frequency, f0 (see Figure2.8), rather than the repetition rate, frep , to ensure that a pulse with the same CEP
is always injected into the amplifier. A Faraday isolator is also inserted, to prevent
optical feedback into the oscillator. The cryogenically cooled amplifier cell is pumped
by a diode-pumped YAG laser (Coherent Corona), delivering 14 W of power at 1 kHz,with a power stability better than 1% rms. The output of the amplifier system is 1.4
mJ at a repetition rate of 1 kHz, with a FWHM pulse duration below 35 fs and an rms
power stability of 0.8 - 1.2 %.

Figure 2.9: Schematic of the CEP stabilized laser amplifier system: MSF, microstructured fiber; PZM, piezoactuated mirror; WP, wave plate; IF, interference filter.

56
Part of the amplifier output (4%) is used for phase detection (using spectralinterferometry, see Figure 2.10) [79]. Frequency-domain detection of the CEP of thehigh-energy pulse is done by focusing part of the output beam into a 5 mm thicksapphire plate to generate a white-light continuum. A 10 mm lithium triborate (LBO)
crystal is then used for doubling the IR component, and the interference signal between
the doubled IR and the short wavelength part of the continuum is detected with a highresolution spectrometer after the wave has passed through an interference filter. The
spectrometer s integration time can be varied from 1 ms to 10 s, allowing for single-shotdetection at 1 kHz.
from
amplifierdoubling
crystal
530nm
1060nm

E F ~ AF (ω )eiφCE

E SH ~ ASH (ω )e(i 2φCE +ωτ delay)

spectrometer

sapphire platecontinuum generation

Figure 2.10: Spectral interferometry for the measurement of amplifier carrier-envelope
phase fluctuations.

For the following measurements, the detected values of rms CEP noise provide
an upper limit, since they include both system and detection noise. Power fluctuationsof the amplifier will introduce CEP fluctuations through the self-phase modulation that
occurs in the sapphire plate used to broaden the spectrum. Interferometric instabilities
will also result in added CEP fluctuations.
Figure 2.11 (top) shows the interference fringes’ visibility in the cases when theoscillator was CEP locked and unlocked versus integration time. Figure 2.11 (bottom)
shows the corresponding rms CEP noise in the case when the oscillator was CEP locked.
The fringe visibility for longer integration times was normalized to single-shot visibility. In these measurements, no active feedback from the output of the amplifier was

57

Figure 2.11: Top, fringe visibility versus integration time of the detector for locked andunlocked oscillators. Bottom, accumulated rms CEP noise corresponding to a CEPlocked oscillator.

implemented. Fringe visibility in the unlocked case drops rapidly. In the locked case,after an initial decrease of 1 to 5 ms integration time, it remains constant for as long as
500 ms. Thus most of the phase noise arises from frequencies greater than ≈ 200 Hz.
The data for 1 s integration time show a modest loss in visibility. However, it should be
noted that noise from the detector (power-fluctuation induced CEP noise plus electronicnoise) becomes important at such a long integration time.
Next, the phase was monitored over long periods of time. Figure 2.12 (top)shows the evolution of the phase-dependent interference fringes measured for more than
30 min. For a single shot, the inter-fringe distance corresponds to a 2π shift. Each point
represents an integration time of 1 ms and was collected at 2 Hz. As was the case for thevisibility measurement, the data were collected without active feedback on the amplifier
output. Figure 2.12 (bottom) shows the results of using the computer that measures
the CEP to supply a sinusoidal voltage signal with a period of ∼ 40 s to the oscillator
locking electronics. This sinusoidal voltage is added to the error signal by an adder

58

Figure 2.12: Evolution of the fringe pattern derived from the output of the amplifier
as a function of time, when (top) the oscillator is phase locked and when (bottom) asinusoidal voltage is applied to the oscillator locking electronics. This voltage is added
to the error signal by an adder electronics box.

electronics box, amplified and sent to the piezo-actuated tilt mirror inside the oscillator.
Such a time-domain modulation of the CEP can be used in conjunction with lock-in
analysis techniques, with no further long-term stabilization of the CEP. The absence ofactive feedback in the amplifier simplifies the design considerably without significantly
limiting usefulness. It also ensures that no additional noise from the amplifier CEP
retrieval algorithm is introduced into the system.
It was also noted during these experiments that long-term stability of the CEP
is correlated to the signal-to-noise ratio of the f-to-2f beat note used to stabilize theoscillator. As coupling into the microstructured fiber drifted, the amplifier CEP drifted.
This correlation can be seen in Figure 2.13.
Active stabilization of this parameter might thus result in an improvement in longterm CEP stability. We investigated several explanations for the excellent long-term
stability of our system compared with previous results. Great care was taken to stabilize

59

wavelength (nm)545

Intensity (a.u.)

525
1.6

1.35
0

time (s)1600

Figure 2.13: Correlation between intensity drop of the beat note from the microstructure
fiber used in the oscillator feedback loop and drift of the spectral interference fringes
recorded after the amplifier. The intensity drop in the beat note leads to a deteriorationof the feedback loop performance.

the pump laser’s power output beyond the manufacturer’s specifications, and a rms noiseof less than 1% was achieved. However, we believe that the main cause of excellent longterm stability is cryogenic cooling of the Ti:sapphire crystal [5], which is unique to thissystem. It is known that cryogenic cooling reduces thermal lensing (by > 2 orders ofmagnitude over room temperature) and allows for higher average power. Calculations
were made to compare the CEP slip in sapphire at different temperatures that were
due to pump power fluctuations [159]. While the effects were an order of magnitude
bigger at room temperature than at cryogenic temperature, they were overall 12 ordersof magnitude too small to produce a significant change in the CEP. We believe that themore important effect of cryogenic cooling is the reduction of beam pointing fluctuations
out of amplifier crystal. As thermal beam pointing drifts can lead to substantial CEPchanges in a misaligned compressor, the reduction of this effect could be an explanation

60
for the good long-term stability of our amplifier.
In conclusion, we have presented what is to our knowledge the first demonstrationof a CEP stabilized, grating-based amplifier system with excellent intrinsic long-term
coherence. The remaining slow drift of the CEP can be easily monitored. We have also
reported the first CEP noise measurements for a grating-based chirped-pulse amplification system that includes single-shot measurements as required for accurate estimationof this noise. Finally, we demonstrated an ability to control and modulate the CEP of
the amplified pulse. The use of a grating-based stretcher and compressor also allows for
scaling to much higher output energies.
Since our work, the CEP stabilization of grating based amplifiers has continued to progress: A slow feedback control of the CEP of a grating-based amplifier wasdemonstrated, by adjusting the effective distance of the gratings in the stretcher of theamplifier [94]. A CEP stabilized amplifier with improved stability, using a grating-based
stretcher-compressor system is now commercially available (KMLabs).

Chapter 3
Generation and temporal characterization of attosecond pulses

This chapter contains materials published in [154] and [152]. In this chapter I
present the first temporal characterization of extreme ultraviolet radiation generated ina noble gas-filled hollow-core waveguide. In particular I concentrate on two regimes of
EUV radiation which both generate pulse durations in the sub-optical-cycle regime (i.e.
radiation shorter than one optical cycle of the driving NIR pulses, which corresponds to2.66 fs for a center wavelength of 800 nm). In the first regime I describe, we generated
and characterized pulses with an envelope of 1.4 femtoseconds, comprised of one or two
attosecond pulses - each shorter than 500 attoseconds. This first regime, in addition toits short duration, has the advantage over other sub-optical cycle EUV radiation demonstrated so far, that its energy is spectrally confined to a width of ∼ 1eV , and therefore
can be used without the need for further spectral filtering by lossy EUV optics. This
radiation is in addition easily spectrally tunable by adjusting the pressure and intensity
in the waveguide. This makes this radiation particularly useful as a pump or probe
pulse in experiments that require state-selectivity. In the second regime we investigated, we could show that primarily single isolated attosecond pulses of 200 attosecond
duration can be generated using NIR driving pulses of 15 femtosecond duration coupled into a hollow-core waveguide filled with low-pressure Argon gas. Again the driving
pulses were not CEP stabilized. These driving pulses are thus significantly longer thanshown in previous work – so far the longest NIR driving pulses that showed evidence

62
for the generation of single attosecond pulses of 650 ± 150 attosecond duration were 7.5
fs long [63]. In both regimes we investigated, we thus combined experimental measurements with careful numerical analysis, to demonstrate that even relatively long-duration,
13−15 fs, carrier-envelope-phase (CEP) unstabilized near-infrared (NIR) pulses can generate extreme-ultraviolet (EUV) radiation confined to sub-optical cycle duration by the
dynamically-changing phase matching conditions in a hollow-core waveguide geometry.
The measurements were made using the laser-assisted photoelectric effect to crosscorrelate the EUV pulse with the NIR pulse. A FROG CRAB analysis of the resulting
traces (photoelectron signal versus photoelectron energy and EUV-NIR delay) was performed using a generalized projections (GP) algorithm, adapted for a wide-angle photoelectron detection geometry and non-CEP stabilized driving laser pulses. In addition,
we performed direct FROG CRAB simulations under the same conditions. Such direct
simulations allow more freedom to explore the effect of specific pulse parameters on
FROG CRAB traces than is possible using the automated GP retrieval algorithm.

3.1

Introduction
To date, sub-femtosecond light pulses have been generated only through theprocess of high-order harmonic generation (HHG). By the uncertainty principle, subfemtosecond light pulses require a bandwidth larger than 1015 Hz, which is larger thanthe entire visible range of the spectrum. In HHG an intense ultrashort laser pulse
is focused into a gas. The interaction between the atoms and laser field is so strongthat a portion of the electron wave packet can escape the atom due to the loweringof the Coulomb potential by the laser electric field. The electron wave packet is thenaccelerated by the laser electric field, and forced back towards the atom as the sign ofthe field reverses. The returning electron wave packet can, with a certain probability,
recombine with the ion and emit higher harmonics of the fundamental laser frequency[87, 93, 26]. This high-order harmonic upconversion of intense femtosecond laser light

63
results in a tabletop-scale source of coherent light in the extreme ultraviolet (EUV) region of the spectrum. This light source has produced the shortest light pulses measured
to-date, making it ideal for observing electron dynamics in atoms, molecules and condensed systems on femtosecond (fs= 10−15 s) or attosecond (as= 10−18 s) timescales.
Simple pump/probe geometries are being developed, in analogy to the well-establishedpump/probe techniques using visible and NIR femtosecond pulses for the study of nuclear dynamics.
To date, considerable effort has been devoted to generating isolated attosecond
EUV pulses using very short, 5 fs, carrier-envelope-phase stabilized driving laser pulses[141]. Such ultrashort laser pulses need meticulous dispersion control over a large frequency bandwidth, and are challenging to propagate through even one meter of air(which will broaden a 5 fs pulse to 12 fs). Moreover, the EUV spectrum that supports
an isolated attosecond pulse consists of a broad continuum. However, many experiments in ultrafast molecular and materials spectroscopy require EUV pulses slightly
longer in duration, in the range of ∼ 1 fs. This is because such pulses can have a sufficiently narrow spectral bandwidth to either initiate or probe the femtosecond dynamics
of specific electronic excited states with reasonable spectroscopic resolution (∼ 1 eV).
Good spectroscopic resolution is required for obtaining initial-state-specific photoelectron spectra in the typically congested EUV spectra of molecules, molecular clusters, or
solids [61, 51, 41, 181, 129, 130, 37]. Therefore, the generation and characterization of
sub-optical-cycle EUV pulses with narrow spectral bandwidth is a topic of great interest
that has remained unexplored to date.
Not only the generation, but also the characterization of sub-optical-cycle EUV
waveforms is challenging. Nearly all current EUV pulse characterization techniques
rely on two-color photoionization, in which an atom is simultaneously irradiated with
EUV and near-infrared (NIR) laser fields and the energy of the resultant electrons ismonitored as a function of the time delay between the laser and EUV fields. In the case64of relatively long EUV pulses (> 10 fs), the EUV pulse duration can be deconvolved fromthe cross correlation measurement provided that the laser pulse duration is accurately
characterized. However, in order to extract the pulse duration of a sub-optical cycle EUV
field from a cross-correlation measurement, both the laser pulse and the cross-correlation
between the EUV and laser fields would need to be measured to an accuracy better
than ∼ 0.05 fs (which is not feasible). The RABBITT (Reconstruction of Attosecond
Beating by Interference of Two-photon Transitions) technique [117] can be used todetermine the temporal structure of the individual attosecond bursts - but not theoverall envelope. Alternatively, the FROGCRAB (Frequency-Resolved Optical Gating
for Complete Reconstruction of Attosecond Bursts) technique [101, 124] has recently
been introduced, which in theory allows for reliable deconvolution of an EUV waveformof any duration. However, this measurement technique has to-date been applied only
to the case of a single isolated EUV burst of 130 as duration [141], where the isolated
nature of the EUV burst considerably simplifies the pulse shape extraction.
Applications of attosecond pulses are only beginning to emerge. Noteworthy
examples include an experiment in which an attosecond pump pulse (∼ 250 attosecond
pulse centered around 90 eV) was used in conjunction with a NIR probe pulse and theN e2+ yield revealed ionization steps on the order of half a driving laser cycle [166].
Another notion of things to come in the future [18] shows that attosecond pulses canalso be used in condensed matter systems: Here, an EUV isolated attosecond pumppulse and a NIR femtosecond probe pulse were used to determine a 100 attosecond
delay between the emission of photoelectrons from localized core states and from theconduction band.
It should be noted here, that manipulation of electron dynamics on the attosecond
time scale does not require the use of isolated attosecond pulses (or the use of attosecond
pulse trains). Pulse shaping techniques of intense NIR femtosecond pulses can be used
to manipulate electron trajectories in the continuum with a precision of 25 attoseconds.

65
The interference of these electron trajectories in the continuum can lead to a usefuloutcome such as control over the shape of the produced high order harmonics [11, 21].
Another example is the excitation of correlated nuclear and electronic wave packets inthe strong-field ionization of D2 . As for high harmonic generation, the electron returns
to the nucleus. Instead of recombining and emitting a photon, it inelastically scatters,
leading to the dissociation to D+ + D. The experiment is repeated using several fundamental laser periods, thus changing the recollision time. From the measured energiesof the D+ fragment, the motion of the nuclear wave packet on the D2+ XΣg potential
curve can be tracked with ∼ 200 attosecond resolution [111].

3.2

Attosecond pulse generation methods
To-date, single, isolated attosecond pulses have been generated only using very

short-duration, 5-7 fs driving laser pulses. Using these very short-duration laser pulses[22, 58] the cycle-by-cycle electric field of the laser pulse changes significantly. The
highest energy EUV radiation is then generated exclusively by the strongest half-cycle(provided the CEP is adjusted appropriately). In this case the discrete harmonic structure disappears at the highest energies and the spectrum broadens into a continuum.
Spectrally filtering to allow only the highest energy harmonic light to pass can thenproduce a single isolated attosecond pulse. This method requires a very short, intense
femtosecond pulse to create the amount of continuum bandwidth required for an attosecond pulse in the strongest half cycle alone (as a rule of thumb a 200 attosecond
pulse requires a FWHM bandwidth of 9 eV assuming a Gaussian spectral shape). The
proposal by Christov et al. [22] showed that 5-fs pulses are required, and indeed isolated
pulses of few hundreds of attosecond duration have been experimentally demonstrated.
The current record is 80 attoseconds while writing this thesis [58].
A variation of this method adds a rapidly changing ellipticity to the driving laser
pulse [141, 20, 25]. The efficiency of high harmonic generation is strong only for linearly

66polarized driving lasers, and falls strongly with ellipticity. In this scheme only a single
half-cycle occurs which has linear polarization and therefore allows generation of highharmonics, whereas the elliptical polarization suppresses HHG in all other half-cycles.
This ellipticity scheme was the first proposal to generate isolated attosecond pulses[25], based on earlier suggestions of the attosecond pulse structure of high-harmonic
generation [43, 59]. The original proposal suggested that driving pulses of 25 fs duration
could be used to generate subfemtosecond pulses. The use of 25 fs driving pulses has
proven to be over-optimistic; nevertheless, polarization modulation of a sub-10 fs driving
pulse can broaden the region of the spectrum over which a continuum is generated, andthus helps to generate shorter-duration pulses.
Experimentally, all implementations of attosecond pulses to-date have used carrierenvelope phase (CEP) stabilized driving pulses of 5 fs duration, with the exception ofsome earlier experimental results that showed evidence for the generation of single attosecond pulses of 650 ± 150 as duration using 7.5 fs long driving laser pulses [63]. In
detailed theoretical studies [48] the reason for generating a single isolated attosecond
pulse using such long driving pulses was explained by ”ionization driven spatio-temporal
reshaping of the intense driving pulse as it propagates through a long, relatively dense
medium leads to XUV radiation which, after spatial and spectral filtering in the far
field, yields an isolated attosecond pulse”.
As CEP stabilized 5 fs pulses are difficult to work with, there is great interestin generating isolated single attosecond pulses using longer driving pulses e.g. by employing two-color laser driving fields, ionization gating, quasi-phase-matching or longwavelength driving lasers [102, 104, 122, 17, 23, 49]. So far, these have been theoreticalsuggestions or spectral measurements, but with no temporal characterization of theemission generated in these longer-duration driving pulse regimes to date.

67

3.3

Attosecond pulse measurements
Characterizing the time structure of either attosecond pulse trains [98, 100] or

isolated attosecond pulses [141, 58] is equally important and technically challenging to
the generation process. There are several reasons for this. First, the generated radiation
lies in the extreme ultraviolet (EUV) region and therefore is strongly absorbed in air or
any material. As a consequence, experiments must be conducted inside a vacuum chamber. Second, as high harmonic generation is a highly nonlinear process, the EUV photon
flux is typically low (≈ 109 photons/pulse at 45 eV). For these reasons, instantaneous
nonlinear effects that are commonly used in the visible region are difficult to access inthe EUV regime. Therefore nearly [143, 110] all current EUV pulse characterization
techniques rely on two-color photoionization, in which an atom is simultaneously irradiated with EUV and near-infrared (NIR) laser fields, and the energy of the resultant
electrons is monitored as a function of the time delay between the laser and EUV fields[142, 56]. Here the EUV radiation creates one or several electron wavepackets by single
photon photoionization. These wavepackets are then modulated by the electric field of
the NIR laser field, leading to sidebands or shifts in the resulting photoelectron spectra (see below). The resulting spectrogram as a function of delay τ and photoelectronenergy ω encodes information about the temporal structure of the EUV pulse.
To extract the temporal structure of the attosecond fields from the spectrogram,different methods have been proposed and some of them have been experimentally implemented [117, 73, 27]. For isolated attosecond pulses that are significantly shorter
than the driving laser field, the “attosecond streak camera” technique has been used[73]. To reconstruct individual attosecond bursts of long attosecond pulse trains consisting of identical attosecond pulses, the “RABBITT” (Reconstruction of Attosecond
Beating By Interference of Two-photon Transitions) technique has been employed. As
originally proposed, RABBITT used the sideband structure to extract the relative phase

68
between harmonic orders, which relates directly to an averaged attosecond pulse structure. However it did not attempt to obtain information on the pulse envelope, e.g.
through analysis of the detailed shape of the sidebands versus energy and delay. A
more generally applicable method is the FROG-CRAB (Frequency Resolved Optical
Gating for Complete Reconstruction of Attosecond Bursts) technique. This technique
was theoretically proposed in [101, 124] and can in theory characterize attosecond fields
of arbitrarily complex temporal structure. We chose this method to characterize recent
experimental data [154] because they were exactly in the transition regime between an
isolated single attosecond pulse and a train of attosecond pulses. That work demonstrated that, by using pulses of ∼ 13 fs duration in a phase-matched hollow-waveguide
geometry, EUV pulses with envelope duration of 1.4 fs and individual pulse structure of< 500 as could be generated. This corresponds to an attosecond pulse ”train” that could
contain ∼ 80% of its energy in a single burst, or consist of two equally strong bursts –the FROG CRAB measurement technique could only determine a pulse envelope andthe structure of the individual attosecond bursts (but not their position) in this case ofa non-CEP stabilized laser.
Despite all the efforts in characterizing experimental attosecond pulses, there arestill unresolved issues in using attosecond pulse retrieval algorithms. Even the mostcurrent approaches fail to recover certain pulse parameters, e.g. do not yet give correctly the relative phase of adjacent EUV pulses [52]. Furthermore, so far no algorithm
correctly includes the final photoelectron kinetic energy dependence in the FROG trace.
This effect can be seen in [141] where the shifted photoelectron energies using the algorithm result in shifts that are too small at high photoelectron energies and too large at
low photoelectron energies. The same effect can be seen in our results when we retrieve
the attosecond pulse using a GP (Generalized projections) algorithm [163, 164] thatneglects the photoelectron kinetic energy dependence. The energy dependence is mostimportant at low photoelectron energies and large ponderomotive shifts. Experiments

69
in molecular dynamics using soft x-ray pulses often employ relatively low energy photons. Thus accuracy in characterizing all wavelength ranges is desirable. We note that
inclusion of the photoelectron kinetic energy dependence should be feasible in future
implementations of the GP algorithm of FROGCRAB, however is not feasible for the
more general PCGP (Principal components generalized projections) algorithm [81].

3.3.1

EUV EUV autocorrelation

EUV pump/ EUV probe experiments are extremely challenging, in contrast towhat is routinely done in conventional geometries with visible/NIR femtosecond pulses.
Nonetheless, an autocorrelation measurement of the 27th harmonic from a Ti:sapphirelaser was performed by the Midorikawa group using two-photon double ionization of
Helium [110]. Two-photon ionization cross sections at this energy are σ2 ∼ 10−52 cm4 s(and therefore similar to two-photon ionization cross sections in the visible region of
the spectrum). The two-photon events/pulse are given by n V σ2 F 2 τpulse where n V
is the number of target atoms in the interaction volume V . Events are limited by theof photons. With the currently available low EUV
low EUV photon peak flux F = numberτpulse ·Area

flux most researchers however choose to temporally characterize the EUV pulses using
two-color cross-correlation methods, where a strong NIR femtosecond pulse (often thesame pulse that generated the EUV radiation) is used to characterize the EUV pulse.
These methods will be described in the next sections.

3.3.2

Laser-assisted photoemission

Nearly [143, 110] all current EUV pulse characterization techniques rely on laser
assisted photoelectron emission. Such techniques were pioneered by Schins and coworkers, who demonstrated laser assisted Auger decay [142], and by Glover and coworkers,
who used the laser assisted photoelectric effect for the first temporal measurements offemtosecond high harmonic radiation [56]. The EUV and fundamental near-infrared

70
fields are focused with an adjustable delay into a gas jet. An EUV photon sets an electron free out of an atom. If at the same time the fundamental laser field is present, thephotoelectron energies will be modified, i.e. the fundamental field acts as a phase shifter
for the electron wave packet. From the detailed shape of the resulting photoelectron
spectrum versus EUV-NIR delay, the temporal structure of the EUV radiation can be
retrieved. Roughly speaking, there are two limiting regimes depending on whether thephotoelectrons are set free by a long EUV pulse train or an isolated attosecond EUV
pulse, as shown in Figure 3.1.
Figure 3.1(a) shows the quantum regime of laser-assisted photoemission: For along EUV pulse, where long means longer than an optical cycle of the NIR field, then the
NIR field periodically modifies the energy of the photoelectron wavepacket in time, anddue to interference between portions of the wavepacket set free at different times, sidebands develop in the photoelectron spectrum. These sidebands are spaced by the laser
photon energy, so one can think of them as being due to absorption or emission of laser
photons during the photionization process. There are two ways in which EUV pulse
durations can be obtained in this regime: (a) The non-interferometric cross-correlation:
As the delay between EUV pulse and fundamental pulse is varied, the sidebands will
be visible as long as the two pulses overlap, i.e. roughly for a range of delays from−tf undamental /2 − tEU V /2 to tf undamental /2 + tEU V /2. So, if the fundamental pulse duration is well known, the EUV pulse duration can be inferred from the temporal extent
of the sidebands. (b) Interferometric cross correlation: Here one makes use of the interference between two pathways leading to the same sideband which causes oscillations in
sideband intensity vs. delay. This sideband oscillation carries information on the spectral phase of the EUV pulse. So from the EUV spectrum the amplitudes and from the
sideband oscillations the phases are known, and the full pulse structure can be reconstructed. Figure 3.1(b) shows the classical regime of laser-assisted photoemission: For
an EUV pulse duration much shorter than half an optical cycle, there is no interference

71

(a)

laser pulse
EUV pulse
Del
ay

hυL
hυL

τ

(b)

Del
ay τ

Figure 3.1: Different regimes of laser assisted photoelectron emission. In both cases
EUV (blue) and fundamental pulse (red) are focused with adjustable delay into a gas
jet. (a) Quantum regime, where the EUV duration is much longer than one cycle of thefundamental light. The photoelectron spectrum (grey) generated by discrete harmonics
of EUV light develops sidebands due to emission/absorption of additional fundamental
photons. Sideband intensities are modulated versus delay due to interference of the 2
pathways indicated by red arrows. (b) Classical regime for EUV pulses shorter than afundamental half-cycle. Here the broad photoelectron spectrum is energy-shifted dueto the momentum imparted by the fundamental laser field.

between different portions of the photoelectron wavepacket. The freed electron will be
accelerated by the laser electric field - this will shift its final momentum (final means

72
when electron is detected at the photoelectron spectrometer, and the laser pulse has
R∞long vanished) by an amount ∆p(tr ) = tr e EL (t0 ) dt0 = eA(tr ), and hence the final
photoelectron energy, as shown in Figure 3.1(b).

Figure 3.2: (a) Adapted from Ref. [63]. In two-color photoelectron spectroscopy,
photoelectrons
R ∞ experience a momentum shift due to the fundamental laser light of∆p(tr ) = tr e EL (t0 ) dt0 , starting from the time tr they are released from the atomby the EUV light. This leads to periodic energy shifts with delay between fundamental
and EUV light. (b) In 90◦ detection geometry, periodic downshifts are observed. (c) In0◦ detection geometry, up- and downshifts are observed. The 2 − π detection geometry
used in this work includes electrons from both cases.

In Figure 3.2 we take a more detailed look at these momentum shifts: In 3.2(a)the momentum shift is shown as a function of the release time of the photoelectron(delay between the EUV pulse and the laser electric field) - it is 90 degrees out of phase

73
with the electric field. In Figure 3.2(b) and (c) the momentum diagram of the process
is shown. The EUV light can eject the electrons according to the differential partial
cross section. Assuming the electrons are ejected on an isotropic momentum sphere(as shown for tr = 0), the electric field then shifts the momentum sphere periodicallyup (tr = T0 /4) and down (tr = −T0 /4) along its polarization direction. The final
momentum depends on both - the momentum shift imparted by the fundamental field,
as well as the direction of photoelectron momentum w.r.t. fundamental electric field.
We specify this direction by the angle θ between final photoelectron momentum andelectric field polarization. We will detect these momentum shifts as energy shifts in aphotoelectron spectrometer. Figure 3.2(b) shows that for θ = 90◦ detection, only energy
downshifts are expected (with period T0 /2), while for θ = 0◦ detection both up- anddownshifts are expected (with period T0 ). The spectrometer used in this thesis has a2 − π detection geometry and thus includes electrons from both cases.
In the following short sections I will briefly review different techniques for attosecond pulse reconstruction based on the principle of laser-assisted photoemission.
While the “Attosecond streak camera” technique is suitable for single isolated attosecond pulses, and RABBITT is suited for long attosecond pulse trains, the FROG CRAB
technique is generally applicable and will therefore be described in more detail below.
“Attosecond SPIDER” is another proposed technique, that opposed to the other methods does not rely on the generation of a photoelectron wave packet as a replica of the
EUV pulse, but therefore requires the generation of a replica of the EUV pulse itself.

3.3.3

Attosecond streak camera

This method [73, 84] is suited for the characterization of an isolated attosecond
pulse. The principle is shown in Figure 3.3. The delay between a single EUV pulse
and the fundamental field is adjusted such that the EUV pulse sits at a maximum of
the fundamental electric field. At this position the vector potential has a maximum

74
positive slope and ”streaks” the photoelectron energies: photoelectrons generated at
the beginning of the attosecond pulse are energy downshifted, while at the end of theattosecond pulse they are energy upshifted. If the attosecond pulse is chirp-free, thephotoelectron spectrum is broadened. A positively chirped pulse is broadened, while anegatively chirped pulse is narrowed. This relation can be reversed by repeating theexperiment Tf /2 later, where the vector potential has maximum negative slope.
Afund(t)NIR vector potentialt
IEUV(t) Delayed EUV pulsestPhotoelectron energy (t)No EUV
chirp

Recorded time-integrated
photoelectron spectra
vs. EUV-NIR delayt
Positive
chirpt
Negative
chirp

−∞

-T0/4

0

T0/4 t− ∞ -T0/4

0

T0/4 Delay

Figure 3.3: Determination of EUV pulse structure from photoelectron spectra in theattosecond streak camera measurement. Red: fundamental vector potential. Blue: EUV
pulse, shown at various delays w.r.t. fundamental pulse. In green, the center frequenciesof photoelectron spectra are shown versus time. For each delay, the experiment records
time-integrated photoelectron spectra, shown to the right. An additional positive/
negative EUV chirp leads to further broadening and narrowing of photoelectron spectra,
revealing the sign of the EUV chirp.

75
3.3.4

RABBITTRABBITT is short for ”Reconstruction of Attosecond Beating By Interferenceof Two-photon Transitions” [109, 117]. RABBITT has been successfully applied to attosecond pulse trains. Here, the EUV electric field in time can be expanded as a sum ofP
harmonics q: Ex−ray (t) = Aq exp(i(ωq t + φq )). To reconstruct the time structure oneneeds the amplitudes Aq ( which are simply obtained with an x-ray CCD camera) andphases φq for all harmonic orders q that make up the pulse. One overall phase is irrelevant, i.e. one only needs to measure all relative phase differences between harmonics.
Laser-assisted photoelectron emission with interferometric stability between the EUV
pulse and NIR pulse allows one to measure these phases from the time dependence ofthe sideband intensity, which oscillates as cos(2ωf undamental τ + (φq − φ(q−2) )) where τ
is delay between EUV and fundamental pulse and (φq − φ(q−2) ) is the phase difference
between q th and (q − 2)th harmonic.

3.3.5

XUV SPIDERThis technique was proposed in [27]. SPIDER is short-hand for ”spectral phaseinterferometry for direct electric-field reconstruction”. For this technique one generates
two replicas of the attosecond pulse, delays and spectrally shifts one of them (by τ andδω, respectively). These two pulses are then detected with an x-ray CCD camera. From
the resulting interferogram S(ω, τ ) = |E(ω) + E(ω + δω) exp(−iωτ )|2 which contains aterm ∝ cos(φ(ω) − φ(ω + δω) + ωτ ), the spectral phase φ(ω) of the attosecond pulse
can be retrieved. The amplitude |E(ω)| of the EUV pulse is measured simply from thespectrum. An inverse Fourier transform of |E(ω)| exp(iφ(ω)) then allows reconstructionof the time structure of the EUV pulse.
A variation of this technique is SEA (spatially encoded attosecond) SPIDER [27],where the two spectrally shifted pulses are interfered in space. An x-ray spectrometer

76
then records spatial interference patterns versus EUV wavelength. This geometry has
the advantage that the required spectral resolution of the x-ray spectrometer can below, as no spectral fringes need to be resolved. Because SEA spider does not use a timedelayed replica, it eliminates concerns about distortions of the replica which travels
through the high harmonic generation medium previously ionized by the first pulse.

3.3.6

Frequency-Resolved Optical Gating for Complete Reconstructionof Attosecond Bursts (FROG CRAB)

FROG CRAB [101, 124] is a generalized method for the reconstruction of attosecond pulses and contains the RABBITT technique and the attosecond streak camera
technique as limiting cases. The idea is to record a photoelectron spectrogram (electron
counts versus energy and EUV-NIR delay) in the presence of the fundamental laser field.
The spectrogram is analyzed using a generalized projections (GP) code to retrieve thetime structure of the EUV pulse. FROG CRAB is the method of choice in this thesis,
and will therefore be described in detail in the following sections.

3.4

Theoretical background: EUV photoionization in the presenceof a NIR driving laser field
FROG CRAB is inspired by the temporal characterization technique FROG,

which is well established for the characterization of short laser pulses in the mid-IR
to UV region of the spectrum [163, 164]. Ultrashort laser pulses in the visible/ NIR
can be straightforwardly measured by making use of nonlinear-optical materials for thisspectral region that operate at easily achievable intensities and have an instantaneous
response. A commonly used nonlinear process is second-harmonic-generation (SHG).
There a beamsplitter is used to split the pulse into two pulses i.e. one creates a replicaof the pulse. This replica can then be delayed w.r.t the pulse in the other arm using adelay stage. The replica thereby serves as a temporal gate, sampling the spectrum of

77
the pulse at varying delay steps. A two-dimensional trace of spectra versus delay steps
is the result. This spectrogram S(ω, τ ) can be mathematically written as
¯Z +∞
¯2
¯
¯
¯
S(ω, τ ) = ¯E(t)g(t − τ ) exp (−iωt)dt¯¯

(3.1)

−∞

where E(t) is the electric field and g(t − τ ) is the gate function which is simplyE(t − τ ) in the case of SHG FROG. From the measured spectrogram the complete
electric field can be determined using iterative Fourier-transform algorithms.
As first discussed in [101, 124], FROG CRAB extends FROG to the EUV andfor attosecond pulses. For completeness we include here the main results of Quéré
et. al. [101, 124] where they describe photoionization of atoms by EUV pulses in
the presence of low-frequency driving pulses. The derivation assumes the strong fieldapproximation (i.e. neglects the effect of the ionic potential on the motion of the electron
after ionization) and the single active electron approximation. First, EUV radiation
creates one or several electron wavepackets by single photon photoionization, which arethen modulated by the electric field of the NIR laser leading to sidebands or shifts
in the generated electron wavepackets. Mathematically the transition amplitude of theelectron wavepacket av (τ ) at a delay time τ from the ground state to the final continuum
state |v > with final electron velocity v is given byµ ·¸¶
Z +∞ 2 0
p (t ) 0
av (τ ) = −idp(t) · Exray (t − τ ) exp i Ip t −
dt
dt
2
−∞
t
Z +∞

(3.2)

Here dp(t) is the dipole transition matrix element from the ground state to thecontinuum state |p >, p(t) = v + A(t) is the instantaneous momentum of the free elecA,
tron in the laser field. Here A(t) is the vector potential such that ELASER (t) = − ∂∂tand Exray (t − τ ) is the electric field of the EUV pulse and Ip is the ionization potentialof the atom. The term in the exponential is the acquired phase in the ground state until
ionization at time t, and the Volkov phase i.e. the integral of the instantaneous energy

78of a free electron in the laser field.
Because there is no general description of the dipole transition matrix element
dp(t) , it is expedient to assume that it takes a constant value independent of energy.
However this could lead to a photoelectron amplitude versus energy being different
from the EUV pulse amplitude. Therefore the ionization cross section versus energy
should ideally be taken into account in the fit process, or the EUV spectrum should be
independently measured by a x-ray spectrometer. The EUV spectrum and photoelectron
spectrum might also differ in phase if there is a phase dependence of the transition dipole
matrix element as a function of energy (e.g. resonances in the continuum).
We can rewrite the amplitude of the electron wavepacketZ +∞av (τ ) = −i−∞exp (iΦ(t))dp(t) · Exray (t − τ ) exp (i(Ip + W )t)dt

(3.3)

where
¶
Z +∞ µA2 (t0 )0Φ(t) = −v · A(t ) +
dt0
2
t

(3.4)

Since we are measuring photoelectron probabilities, the modulus square of theamplitude of the electron wavepacket, |av (τ )|2 needs to be compared to the spectrogram
S(ω, τ ). The one-by-one comparison shows that the gate function g(t − τ ) of S(ω, τ )corresponds to the exp (iΦ(t)) term in |av (τ )|2 :g(t) = exp (iΦ(t))(3.5)

This term corresponds to a phase modulation of the electron wavepacket induced by the
NIR dressing laser, which serves as a temporal phase gate for measuring the durationof the EUV pulse.
Finally we express the phase with experimental observables as a sum of threecontributions:Φ(t) = Φ1 (t) + Φ2 (t) + Φ3 (t)

(3.6)

79
Z +∞
Φ1 (t) = −p
Φ2 (t) =t

Up (t)dt(3.7)

8W Up (t)cos(θ)cos(ωL t − φCE )
ωL

(3.8)

Up (t)sin(2ωL t − 2φCE )
2ωL

(3.9)

E2
exp(−4 ln 2(t/τ )2 )4ωL2(3.10)

Φ3 (t) = −where
Up (t) =is the ponderomotive potential, W is the final photoelectron kinetic energy, ωL is thelaser angular frequency, and φCE is the fundamental carrier envelope phase, θ is theangle between the laser polarization direction and the final photoelectron velocity.

3.5

Generalized projections (GP) algorithm for FROGCRAB
We start by using the generalized projection (GP) algorithm to retrieve the EUV

electric field. This iterative Fourier-transform algorithm converges to a solution by
iteratively optimizing between two constraints - one in the frequency and one in the time
domain. In the frequency domain, the calculated FROG trace amplitude is replaced by
the square root of the experimental trace S(ω, τ ), and in the time domain a new guess
for the electric field is obtained by minimizing the error between a newly created signal
0 (t, τ ).
field Esig (t, τ ) and the signal field obtained in the last iteration Esig

A schematic of the procedure is shown in Figure 3.4.
First, a random Exray (t) is generated. Second, a signal field
Esig (t, τ ) = Exray (t − τ ) exp(iΦ(t))(3.11)

is generated. It is important to note here that all current implementations of the
GP algorithm, including ours, replace the final photoelectron kinetic energy W in Eq.

80
START:
random Exray(t)Asig (ω ,τ )Gate(τ )While Zerror, Gerror > error boundZerror
Generate new Exray(t)calculate
Esig (t ,τ )Esig (t ,τ )FFT (t → ω )FFT −1 (ω → t )Esig (ω ,τ ) =Asig (ω ,τ ) exp(iφ (ω ,τ ))Esig (ω ,τ ) exp(iφ (ω ,τ ))GerrorFigure 3.4: Basic schematic of GP algorithm.

(3.8) by W0 , the photoelectron center energy - we will discuss consequences of thisapproximation below. Third, Fourier-transforming into the frequency domain yields
Esig (ω, τ ). Fourth, the amplitude of Esig (ω, τ ) is replaced by the amplitude Asig (ω, τ )of the experimental Frog trace data S(ω, τ ). Fifth, we perform the inverse Fourier0 (t, τ ). Sixth, we improve our guess for E
transform back into time domain Esig
xray (t) by

minimizing the error between a newly created signal field and the signal field obtainedin the last iteration. Seventh, the newly generated Exray (t) is used as input for a newsignal field, which brings us back to the second step of the loop. The retrieval algorithm
is run until the errors in the frequency domain
v
u
N ¯
¯2
u 1 X
¯ 2
¯
2
A
(ω
,
τ
)
−
µ|E
(ω
,
τ
)|
Gerr = t 2¯ sig i j¯
sig i jNi,j=1

and in the time domain(3.12)

81

N
X
¯
¯2
0
¯Esig (ti , τj ) − Esig
Zerr =(ti , τj )¯(3.13)

i,j=1

are lower than a specified limiting value. Here µ is a real normalization constantthat minimizes Gerr and N x N is the array size.

3.6

Modifications to the GP algorithm
Our experimental setup described above uses a magnetic bottle time-of-flight

spectrometer that collects a large range of final electron momenta corresponding toangles from 0 to 90 degrees. Furthermore, the CEP of the pulses is not stabilized.
Both these features require modifications to the GP algorithm. The reason lies in thedependence of the gate function (3.5) on the angle θ and on the carrier-envelope phaseof the NIR pulse, as seen in equations (3.3) to (3.10) in section 3.4. So, in essence one
must run the algorithm with different gate functions in parallel, and do appropriate
averaging when comparing with experimental data. In addition, the resolution of thephotoelectron spectrometer should be included to take into account any broadening of
the spectrum which leads to retrieved pulse durations systematically shorter than theactual pulse duration. In this experimental work, we use a very conservative value forthis resolution, and thus obtain a result that is a realistic upper limit of pulse duration.
The lower limit can be determined by the transform limit of the EUV spectrum.
Figure 3.5 shows how the GP algorithm is modified to take into account the 2 − πdetection geometry and non-CEP stabilized NIR pulses.
First, to take into account the fact that we make no attempt to CEP-stabilize
our driving laser pulses, we take into account two gate functions - one with the absolute phase set to zero degree and one with the absolute phase set to 180 degrees. These
CEP values correspond to ”cosine” and ”minus cosine” IR pulses which lead to identicalconditions for HHG generation in a noble gas. Our results below show that the experi-

82
(θ )
(θ )
GateCEP=0 (τ ) GateCEP =π (τ )START:
random Exray(t)Asig (ω ,τ )While Zerror, Gerror > error boundAverage Zerror over CEP=0 and π
and over angles θ;
Generate new Exray(t)For
θ=0:90o

calculate
Esig ,0 (t ,τ )Esig ,0 (t ,τ )Esig ,π (t ,τ )calculate
Esig ,π (t ,τ )FFT −1 (ω → t )FFT (t → ω )

2
2
Asig
(ω ,τ ) − Esig ,0 (ω ,τ ) exp(iφπ (ω ,τ ))Esig ,π (ω ,τ ) =Esig ,π (ω ,τ ) exp(iφπ (ω ,τ ))Esig ,0 (ω ,τ ) =2
Asig(ω ,τ ) − Esig ,π (ω ,τ )2

exp(iφ0 (ω ,τ ))Esig ,0 (ω ,τ ) exp(iφ0 (ω ,τ ))2

Average Esig (ω ,τ ) over CEP=0 and π, and over angles θ
GerrorFigure 3.5: Schematic of GP algorithm adapted to wide-angle photoelectron detection
geometry and non-CEP stabilized driving laser pulses.

mental data are quite well described by this procedure. The reason why only these twovalues of CEP are required to achieve good agreement is that the NIR beam (whichis the same beam that generated the EUV radiation) is temporally synchronized with
the EUV radiation due to the EUV generation process itself. However if multiple EUV
bursts are present, their relative strengths (amplitudes, not their timing) could changewith CEP. In our case, if for certain CEP values multiple bursts were generated, wewould observe this as a modulation of the photoelectron spectrum, as shown in the simulations presented in Fig. 3.22. Experimentally however, we observe only a very small
amount of modulation (see Fig. 3.17 and Fig. 3.22), meaning either that only in a small

83
fraction of laser shots multiple EUV bursts are generated, or that in every shot only
very small side bursts are generated along with the main burst. The synchronization is
also well-demonstrated by the fact that we clearly see interferometric modulation of thephotoelectron energy data versus delay (see Fig. 3.19 (a)). This is also not any moreof an approximation than that used in any other attosecond pulse measurement. All
measurements, whether they be for isolated pulses or pulse trains, show this interferometric synchronization [100, 63]. Furthermore, at the level of the instantaneous electricfield of the driving laser, CEP fluctuations look identical to intensity fluctuations in thelaser pulse, and recent theoretical calculations have corroborated the insensitivity ofthe pulse generation process to intensity variations [141]. Thus, our presumption thatthe attosecond pulses in the train are well-synchronized with the fundamental electricfield, with the exception that the direction of the field oscillations may flip randomly,
is well justified. The remaining question, which we address below, is whether the averaging over 2 CEP phases creates significant deconvolution ambiguities compared witha CEP-stabilized case.
We therefore apply the algorithm simultaneously to two signal fields - one with the
CEP set to 0 degrees and one with CEP 180 degrees. Instead of replacing the amplitudeof Esig (ω, τ ) by the amplitude of the experimental FROG CRAB trace Asig (ω, τ ), we
replace the amplitude of the signal field with CEP 0 radians |Esig,0 (ω, τ )| with an
expression containing the amplitude of the experimental FROG CRAB trace Asig (ω, τ )¯p¯¯¯and the amplitude of the signal field with CEP π radians ¯ Asig (ω, τ )2 − |Esig,π (ω, τ )|2 ¯.
An analogous replacement is made for |Esig,π (ω, τ )|. This is the essential step of driving
both signal fields to converge to a combined signal field describing the experimental
FROG CRAB data. To obtain the Gerr we calculate the rms error between the combined
signal field|Esig (ω, τ )|2 =¢1¡|Esig,0 (ω, τ )|2 + |Esig,π (ω, τ )|22(3.14)

84
and the experimental FROG CRAB trace. In the next step we Fourier-transform
both signal fields back into time domain, yielding Esig,0 (t, τ ) and Esig,π (t, τ ). Two newguesses for the EUV field Exray (t) are calculated. The average of the two EUV fields is00
taken and used to construct two new signal fields Esig,0(t, τ ) and Esig,π(t, τ ). The Zerr

is calculated for both CEP 0 and π according to Equation (3.13), and is then averaged.
Next we discuss how to adapt the algorithm to include the dependence of the gate
on the angle between the laser polarization and the final photoelectron velocity. To thisend we implement a for-loop in which for each angle, both signal fields |Esig,0 (ω, τ )| and|Esig,π (ω, τ )| are calculated. The Gerr is then calculated with the average signal fieldcalculated as a sum over different anglessEsig,CALC (ω, τ ) =

´
X³
θ
θ
|Esig,0(ω, τ )|2 · prob(θ) + |Esig,π(ω, τ )|2 · prob(θ)(3.15)

θ

whereprob(θ) = sin(θ) · σ(θ)/

X

sin(θ) · σ(θ)(3.16)

θis the probability containing the geometrical weight factor sin(θ) for the photoelectron
distribution as well as the differential partial cross section σ(θ) for the detection gas
used [13]. We also generate a for-loop to calculate the Zerr for all angles and we average
the Zerr by calculating
Zerr =

X

Zerr (θ) · prob(θ)(3.17)

θThe Exray (t) is also averaged
Exray (t)ave =X

Exray (t, θ) · prob(θ)(3.18)

θThe resolution of the spectrometer can be included as follows. After calculating
the new signal fields Esig,0 (t, τ ) and Esig,π (t, τ ) in time, they are fourier-transformed
into the frequency domain and convolved with the square root of the resolution functionof the photoelectron spectrometer. The convolved signal fields are Fourier-transformed
back into the time domain. When in the next step the magnitude of |Esig (ω, τ )| is85
replaced (see Fig. 3.5), the information about the convolution is preserved in the phaseof Esig (ω, τ ), which remains unchanged. Empirically we found two further methods for
improving the convergence of the algorithm: for every iteration, we vary the delay ofthe experimental trace by a fixed number of single delay steps to minimize the Gerr .
We also change the sign of the spectral phase of Exray every ≈ 100 iterations. Only thecenter 90% of the delay range of the calculated FROG CRAB trace is used to calculate
the Gerr . This is done to avoid numerical artifacts that occur at the calculated edges.
3.6.1

Atto- and harmonic chirp

Before turning to experimental results, I briefly review two kinds of phase contributions which exist for EUV radiation, called attochirp and harmonic chirp [167].
The harmonic chirp is associated with the second order temporal phase of an EUV∂ 2 φqpulse, which for harmonic order q is defined as bqj = − ∂t2j (j refers to EUV radiation
generated from the short or long electron trajectory) and is given byq

I0 ∂φjbqj ≈ qbf und + 8(ln 2) 2
τ0 ∂I

(3.19)

Here, bf und is the quadratic temporal phase of the fundamental light defined by φf und (t) =−ωt−bf und t2 /2, I0 and τ0 are the fundamental intensity and duration, respectively. The
harmonic chirp is then given by the second order spectral phase
bqj
∂2φ
= q 2
∂Ω2
(bj ) + 16(ln 2)2 /(∆t)4(3.20)(∆t is the EUV pulse duration). The harmonic chirp thus has the same sign as bqj . In
∂φq

the absence of a fundamental chirp it is the same sign as ∂Ij , which is negative, bothfor the short (small negative value) and long (large negative value) trajectory (Figure
1 in Ref. [167]). On the other hand, if the fundamental chirp term is dominant, thenthe harmonic chirp will have the same sign as the fundamental chirp.

86

Figure 3.6: Taken from Varju et al. [167]: Harmonic and atto chirps in frequency andtime domain. (a) Spectral intensity (purple, left scale) and phase (solid blue, rightscale) for a group of 5 harmonics. (b) Corresponding temporal intensity (purple, leftscale) and phase (solid red, right scale). The harmonic chirp corresponds in frequency
domain to a quadratic behaviour around each harmonic (solid blue line), and in time
domain to a slow quadratic drift of the central phase (dashed blue line). The atto chirp
corresponds to a quadratic drift of the spectral phase from one harmonic to the next
(dashed red line), and a fast quadratic variation in time domain around each attosecond
pulse (solid red line).

The atto chirp is given by
batto =

∂ 2 φqj∂q 2∂ 2 φq( ∂q2j )2 + 16(ln 2)2 /(∆Ω)4

where ∆Ω is the spectral bandwidth of the EUV pulse.

(3.21)∂ 2 φqj, and hence the∂q 2

attochirp, is positive for the short trajectory, and negative for the long trajectory (Figure

87
2 in Ref. [167]). The two kinds of chirps are illustrated in Figure 3.6, taken from [167].

3.7

Experimental setup and photoelectron detection geometry

Amplifier30 fs

Ar filled Hollow Waveguide
spectral broadening
Chirped Mirrors
pulse compression

X-ray CCD

Al filter onnitrocellulose
foil

10 fs
HHG
Waveguide

Adjustable delay
for EUV-IR
crosscorrelation
Grating

Gas jetTime-of-flighte- spectrometer

Figure 3.7: Experimental setup for EUV pulse generation and temporal characterization
via photoelectron energy resolved two-color cross-correlation using a NIR pulse.

Our experiment, shown in Fig. 3.7, starts with 30 fs, 2 mJ laser pulses froma cryogenically-cooled 2 kHz Ti:Sapphire laser amplifier [5]. We use a 1 m long, 400µm diameter hollow waveguide filled with Argon gas to broaden the laser spectrum by
self phase modulation (SPM fiber) [113, 149]. To prevent defocusing of the laser pulses
at the entrance of the SPM fiber, we use a pressure gradient of 0 Torr at the inputand ∼ 300 Torr at the output of the fiber. We then temporally compress the pulses
using commercially-available negatively chirped mirrors (Layertec −40 f s2 per mirror
bounce). We obtain pulses of 10 − 15 fs duration centered at λ ≈ 740 nm, and focus

88them into a 150 µm diameter, 3.5 cm long hollow-core waveguide (including two 0.5 cm
long end sections for differential pumping) filled with Argon gas [135], in which the highharmonic radiation is generated. We estimate an intensity in the fiber of ∼ 5.7 · 1014
W/cm2 , and the Argon pressure was ≈ 10 torr [152]. We note that the coupling of
the fundamental light into the fiber was well-optimized (80% coupling efficiency) [152],
resulting in very small power loss inside the fiber, and an excellent near-T EM00 output
mode. This indicates near-perfect coupling to the fundamental EH11 fiber mode. The
spectra of the fundamental radiation after the fiber showed only a small amount ofblue-shift compared to the one before the fiber, indicating that only a small amount of
temporal reshaping of the fundamental pulse took place in this low-pressure regime.
To temporally characterize the EUV pulse, we employ an interferometric, photoelectron energy resolved EUV - NIR cross correlation geometry [36]. The EUV andfundamental driving pulse are focused into a Neon gas jet, and a cross-correlation signal is obtained from the generated photoelectron spectra as the relative delay between
the two pulses is varied. The delay line makes use of the different divergences of thefundamental and the EUV beam exiting the HHG fiber. The low divergence, central
EUV beam passes through a small circular Al filter suspended in a Kapton filter. The
annular fundamental beam, which passes around the Al filter, is reflected by an annularmirror, while the central EUV beam is reflected by a Mo/Si mirror that is mounted ona closed loop piezoelectric transducer (S-325 tip/tilt piezo and z-axis positioner, Physik
Instrumente). The two time-delayed light fields are then focused onto a Neon gas jet.
The photoelectrons ejected from Neon by the EUV beam are then detected using a magnetic bottle time-of-flight spectrometer [86] and a multichannel plate (MCP)
detector in a Chevron configuration. This spectrometer has a 2 π detection solid angle
i.e. photoelectrons parallel and perpendicular to the laser polarization (which points
towards the MCP) are detected. To characterize the EUV spectrum separately, we use
a home-built spectrometer consisting of a concave grating (ROC 1 m, 1200 gr/mm) and89
an x-ray CCD camera (100 x 1340 pixels, Roper Scientific), directly following the highharmonic generation hollow-core waveguide.

3.7.1

Magnetic bottle time-of-flight spectrometer, electronics and dataacquisition

Gas jetSN
e-B-field
EUV
beam

magnetic coil

MCP

Figure 3.8: Magnetic bottle time of flight spectrometer. Electrons from photoionization
in a gas jet are guided towards a MCP detector by inhomogeneous fields. The field
geometry ensures adiabatic parallelization (see text) of all trajectories that had an
initial velocity component towards the MCP, providing 2 − π collection and a time-of
flight proportional to the initial photoelectron energy.

Here the principle of the magnetic bottle time-of flight spectrometer used in thischapter is described [86] (see Figure 3.8). This type of spectrometer was chosen as itallows time-of-flight detection of electrons emitted into 2 − π solid angle, allowing fast
data acquisition even under conditions where in total few electrons per laser shot are
created. It has been rebuilt based on the design in Emily Gibson’s thesis [55]. However,an additional larger coil was added on the top of the spectrometer. The additional coilhad ∼ 100 windings (Kapton insulated square wire gauge 14) and an inner diameterof 16 cm. The reason for this additional coil is that without it, the magnetic field
drops toward zero at the MCP detector (see Figure 3.9). The additional coil lead to anincrease of electron counts by one order of magnitude.

90

1

B (Tesla)

0.1
0.01

total magnetic field w/o extra coilfield from permanent magnet
field from solenoid
coil
coil
Total field including extra coiltube start, tube end

MCP

1E-3
1E-4
0
100
200
300
400
distance from permanent magnet (mm)Figure 3.9: Magnetic fields of the time-of-flight photoelectron spectrometer (in log
scale). Black symbols: Total magnetic field without additional coil. Red line: calculated total field including the extra coil. The drop-off at the MCP position is avoided,
enhancing electron counts by a factor of 10.

The setup is shown in Figure 3.8. To achieve 2 − π collection and time-of-flightdetection simultaneously, the gas jet is placed in an inhomogeneous magnetic field created by a strong permanent magnet (NdFeB). This magnetic field goes over into a
homogeneous field created by a solenoid, which extends through the time of flight tube
to the electron detector, two microchannel plate (MCP) detectors in a Chevron configuration. This total magnetic field configuration initially forces the photoelectrons
on tight circular orbits in the plane transverse to the axis towards the detector, withthe electron trajectory radii given by ri = mvperpendicular /(eB). As the field decaysaway from the permanent magnet and becomes homogeneous, the electron trajectories are bent adiabatically to become almost parallel to the field lines, with the fip
nal electron radii given by rf = ri · Bi /Bf . The parallelization can be understoodfrom the conservation of energy, as well as of angular momentum about the field axis:

91
Lz = mvperp r = const, where vperp = ωr with the cyclotron frequency ω = eB/m.
2
It follows that vperp/B = const, i.e. vperp decreases with decreasing B. Energy conq
2
servation then demands that vz = v 2 − vperp
increases with decreasing B, and theelectron trajectories get parallelized. The ”parallelized” electrons have the same timeof-flight for the same total velocity v. Good energy resolution is thus ensured if theparallelization takes much less time than the time spent in the drift tube.
Care has to be taken that the adiabaticity parameter is kept below unity. It iszdefined by χ = 2πmv
| dB
dz |, which is the fractional change in the field that the electroneB 2zexperiences in one cyclotron orbit. In the design a compromise has to be found between
a low adiabaticity value (large Bf preferred), good energy resolution (low Bf preferred)
and that the electrons hit the active area of the detector (large Bf preferred). The
adiabaticity parameter in the final design remained below 1.5 everywhere inside thespectrometer.
The laser polarization for all experiments in this chapter was chosen parallel tothe time-of-flight axis.
In figure 3.10 I show a sketch of the TOF apparatus and the electronics for processing of photoelectron counts from the MCP detector. The MCP signal was separated
from the high-voltage in a bias tee. A 1.1 µs delay was inserted using a low loss/low
dispersion coaxial cable to temporally separate the signal from electromagnetic noise,
associated with the pockels cell switching for the amplifier pulse. An electronic amplifier/timing discriminator provided the ”stop” signal for the ACAM timing board(the ”start” signal was provided by a fast photodiode recording scattered light fromthe amplifier pulse). The data collected with the ACAM PC board were acquired anddisplayed with a user interface written in Labview. This program also controlled theposition (delay) of the closed-loop piezoelectric transducer, as well as allowing for the
optimization of photoelectron counts using the tip/tilt degrees of the piezo. After alignment was completed the program allowed automated acquisition of a full FROG CRAB

92

HV 2kV

TimingACAM
Bias 1GHz
amplifierdiscriminatortiming
board
tee
stop
NIM start
1.1µs delay

MCP

to
TTL
User
interface

60 l/s
turbo
pump

S N

1GHz
photodiodeEUV-NIR
delay control

Figure 3.10: Electronics following the photoelectron spectrometer setup.

spectrogram. Figure 3.11 shows the Labview interface for Windows XP.
Figure 3.12 shows an example of a photoelectron spectrogram demonstrating thegood resolution of the spectrometer. To quantify the resolution, the widths of photoelectron peaks were compared to the widths of the corresponding harmonics recorded
simultaneously using an x-ray CCD camera in a separate measurement. This yieldedan estimate of the photoelectron spectrometer resolution of 0.73 eV.

93Energy (eV)Figure 3.11: Labview interface for automated acquisition of photoelectron spectrogramsin Windows XP.

25
20

75

80

85

90

95

100

105

Delay (fs)Figure 3.12: Photoelectron spectrogram demonstrating the good resolution (≈ 0.7 eV
at ≈ 22 eV determined in a separate measurement) of the spectrometer: Sidebands andindividual harmonics are clearly separated.

3.8

Temporal characterization of attosecond waveforms in the suboptical cycle regime
In this section, I present the first temporal characterization of sub-optical cycle

EUV pulses generated in a hollow waveguide [154, 140]. This new generation scheme
allows us to use significantly longer driving laser pulses, of 13 fs in duration, than

94
have been used for sub-optical-cycle EUV generation to date. Such 13 fs driving pulses
can be generated by standard ultrafast laser pulse compression techniques. We use
two independent techniques to extract the complex EUV field: an iterative step-bystep reconstruction based on a constrained number of physical parameters and error
minimization between the experimental FROG CRAB trace and a simulation based on
the expression given in [101, 124], and an unrestricted FROG CRAB pulse retrieval
algorithm. Both methods independently show that the generated EUV pulse consists ofa very short train of moderately-chirped 470 attosecond pulses, with bursts spacedby ∼ 1.3 fs with the total energy contained within a 1.4 fs FWHM (full-width at
half-maximum) pulse envelope. Moreover, we show that the EUV field is near the
Fourier-transform limit, with a narrow spectral bandwidth where ∼ 64% of the energy
is contained within a single harmonic peak of 1.1 eV FWHM. Finally, the EUV pulse
can be tuned over an energy range between 38 eV and 48 eV by adjusting the driving
laser intensity and the gas pressure in waveguide. Because of the sub-optical-cycle
pulse duration, narrow bandwidth, ease of tunability, and greatly simplified generation
scheme, this source will have many applications in probing electron dynamics with state
selectivity in molecular systems and materials.
I would like to note here that the generation of such spectrally narrow EUV
spectra, consisting predominantly of a single harmonic, is not restricted to short driving
pulses. I have observed such spectra even with extremely long driving pulses (transformlimit of 45 fs). In this case individual harmonics become very narrow, indicating a very
long EUV pulse envelope. The generation of such spectra appears to be related to thedetails of the alignment of the fundamental beam into the HHG fiber, and hence maybe
to the spatial mode profile in the fiber. The negative dispersion of the EUV radiationthat I observed in [154] could be consistent with phase matching of the long trajectory,
that maybe occurs under special conditions in the fiber.
Our experiment starts with 30 fs laser pulses from a cryogenically-cooled 2 kHz

95
Ti:Sapphire laser amplifier, similar to the ultrafast laser amplifier systems present inhundreds of labs worldwide. We use a 1 m long, 400 micron diameter hollow waveguidefilled with Argon gas to broaden the laser spectrum, and temporally compress the pulses
using commercially-available negative chirped mirrors. We then focus the 13 fs, 2 ×1014 W cm−2 pulses into a 2.5 cm long, 150 micron diameter hollow-core waveguide [135]filled with Argon gas, in which the high harmonic radiation is generated. To temporally
characterize the EUV pulse, we employ an interferometric EUV - NIR cross correlationgeometry [36]. The EUV and fundamental driving pulse are focused into a Helium gas
jet, and a cross-correlation signal is obtained from the generated photoelectron spectraas the relative delay between the two pulses is varied. The delay line makes use of
the different divergences of the fundamental and the EUV beam. The low divergence,
central EUV beam passes through a small circular Al filter suspended in a nitrocellulose
filter. The annular fundamental beam, which passes around the Al filter, is reflectedby an annular mirror, while the central EUV beam is reflected by a Mo/Si mirror thatis mounted on a piezoelectric transducer to introduce a variable delay between thefundamental beam and the EUV beam. The Mo/Si mirror reflectivity is centered at∼ 47 eV with a FWHM ∼ 13 eV, so that all harmonics generated in the waveguide arereflected. The photoelectrons ejected from Helium by the EUV beam are then detectedusing a magnetic bottle time-of-flight spectrometer and a multichannel plate (MCP)
detector. This spectrometer has a 2 − π detection solid angle[86] i.e. photoelectrons
parallel and perpendicular to the laser polarization (which points towards the MCP)
are detected.
Figure 3.13(a) shows the experimental cross-correlation data. At large time delays between the EUV and NIR pulses, the photoelectron spectra are generated by
the EUV light alone. The photoelectron peak generated by the dominant harmonic isclearly visible, as well as two adjacent smaller photoelectron peaks generated by thetwo adjacent weaker harmonics. When both EUV and fundamental beams are present,

96

- 1 0

- 1 0

-10

a)

3.0
2.5

- 8

- 6

- 4

- 2

0

2

4

6

8

1 0

b)

Counts (a.u.)

Photoelectron Energy (eV)

18
20
22
24
26
18
20
22
24
26
18
20
22
24
26

2.0

tunable

1.5

HH27

1.0

- 8

- 6

- 4

- 2

0

2

4

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8

c)
-8

HH29

d)

1 0

0.5
35

-6

-4

-2

0

2

4

6

8

HH31

40

45

50

55

Energy (eV)60

Delay (fs)Figure 3.13: (a) Experimental photoelectron spectrum as a function of time delay between the EUV and IR pulses, when these pulses are focused simultaneously into He gas.
(b) FROGCRAB simulation of the data in (a) based on theory presented in [101, 124].
(c) FROGCRAB trace obtained from a generalized projections (GP) algorithm. (d)EUV spectrum of the pulse that generated the photoelectron spectrum shown in (a).
The energy tuning range is indicated. Tuning of the energy is achieved by changing thepressure and intensity inside the HHG waveguide.

sidebands occur due to the absorption of an EUV photon simultaneous with absorption
or emission of a fundamental photon. The sidebands are modulated at a period corresponding to half the fundamental laser cycle. In the following, we use the FROG CRAB
technique for a careful analysis of our data. FROG CRAB is inspired by the temporalcharacterization technique FROG, which is well established for the characterization ofshort laser pulses in the mid-IR to UV region of the spectrum [?, 164]. The temporalgate for FROG is usually an amplitude gate. Instead of an amplitude gate, FROG
CRAB uses the fundamental field as a phase gate that modulates the electron wave
packet ionized by the EUV beam. It is established that for most conventional FROG
techniques [163], spectrograms will have a certain shape depending on the phase of theE-field to be measured. One might expect that the phase-gate used in FROG CRAB
might generate nonintuitive traces [101, 124]. However, as we show below, this is not
the case.

97First, to gain intuitive insight in the properties of the generated radiation, as
well as in the characteristic features of the FROG CRAB trace, we perform an iterative
error minimization between the experimental FROG CRAB trace and a simulation. The
results of this first analysis will be later fully confirmed by a second, independent analysis
using an unrestricted pulse retrieval algorithm. To generate simulated FROG CRAB
traces, we employed the strong-field-approximation expression given in [101, 124]. We
adapted it to our experimental case where photoelectrons are detected over a 2 − π solid
angle, by averaging the photoelectron distribution for different angles including botha geometrical weighting as well as the differential partial cross section for detecting
photoelectrons from Helium. Our FROG CRAB trace is the addition of two traces forthe fundamental light, a cosine and minus cosine waveform. The reason is that we do
not need phase stabilized laser pulses, and the conditions for generating high harmonics(phase-matching and recollision) are the same for both waveforms. For each delay step,
photoelectrons are acquired for multiple laser shots, and therefore can contain signal
from both waveforms.

Photoelectron
Energy (eV)

18

a)

D2 18

b)

D3 18

20

20

20

22

22

22

24

24

24

26

26

26

-2

-1

0

1

2

-2

-1

0

1

2

c)

-2

D4

-1

0

1

2

Delay (fs)Figure 3.14: Simulated FROGCRAB data, when higher dispersion orders are artificiallyintroduced into the EUV field: (a) 2nd order D2, (b) 3rd order D3, (c) 4th order D4
dispersion. Intuitively, the sideband shape shows the group delay of the EUV light,
indicated by black lines.

Before turning to a detailed analysis of our EUV radiation using FROGCRAB,
we first show that, although FROG CRAB uses a seemingly complex phase modulation

98
gate, considerable intuition about pulse characteristics can be obtained from the shape ofthe sidebands. To demonstrate this, we apply individual dispersion orders to artificiallyconstructed EUV bursts, similar to those generated in our experiment. Sample resultsof FROG CRAB traces are shown in Fig. 3.14, plotted over a delay range of two
fundamental laser cycles. Figures 3.14(a) to 3.14(c) show that the shape of the sidebands
changes significantly depending on whether 2nd order phase D2 (Fig. 3.14(a)), 3rd orderphase D3 (Fig. 3.14(b)) or 4t h order phase D4 (Fig. 3.14(c)) is added. FROG CRAB
traces can also indicate the sign of the dispersion order, because for opposite signs ofdispersion, the sidebands are inverted along the time delay axis.
We now turn to a detailed analysis of our experimental FROG CRAB data. To
construct the EUV electric field for the simulated FROG CRAB trace, we start with the
EUV spectrum shown in Fig. 3.13(d), recorded using an x-ray spectrometer and CCD
camera. This EUV spectrum is then deconvolved with the Gaussian x-ray spectrometer
resolution function of 0.38 eV FWHM, determined by a separate measurement using
spectrally narrow harmonics. (Using the measured EUV spectrum without deconvolution would underestimate the pulse duration by ∼ 5%). The deconvolved EUV spectrum
is then multiplied by the transfer functions that relate the measured EUV spectrum tothat incident on the detection gas. A spectral phase, described below, is added to
the EUV spectrum E(ω), before transforming into the time domain. The calculated
FROGCRAB trace is finally convolved with the measured photoelectron spectrometer
resolution function of width ∆E = 0.7 eV. This photoelectron spectrometer resolution
E imposes an upper limit of approximately h · 0.44/∆E (h is Planck’s constant) on theenvelope duration that can reliably be measured. With the current resolution, we cancharacterize pulse durations up to 2.5 femtoseconds.
As shown above, we can retrieve higher order spectral phases with FROG CRAB.
Therefore, in Fig. 3.15(a), we vary the 2nd order phase and compare the RMS (rootmean-square) deviation of the experimental and calculated FROG CRAB trace withinPhotoelectron Energy (eV) Photoelectron Energy (eV)106 RMS deviation

99
74.5

a)

71.9

73.5

b)

180

c)

160

71.7

140
72.5
71.5
-0.05 -0.04 -0.03 -0.02

71.5

120

71.3

100

18

1.0

-0.01 -0.006 -0.002

D3 (fs3)

D2 (fs2)

d)

1.4

τ

1.8

2.2

2.6

envelope FWHM (fs)

e)

20
22
24
26
-2

18

-1

0

1

2

-2

Delay (fs)

-1

0

1

2

-1

0

1

2

g)

f)

20
22
24
26
-2

-1

0

1

2

-2

Delay (fs)Figure 3.15: RMS deviation between the FROG CRAB simulation and the experimental
cross-correlation trace as the parameters of the simulated pulse are varied: (a) Varying
the linear chirp D2, (b) Varying the quadratic chirp D3, (c) Varying the EUV pulse
envelope. (d) experimental FROG CRAB data, (e) FROG CRAB data simulated using
the optimized values of D2, D3 and EUV pulse envelope of 1.4 fs. (d, e) are zoom-ins of
the centers of Fig. 3.13 (a, b). (f), (g) simulated FROG CRAB data using the optimized
values of D2, D3 but when the EUV pulse envelope is changed from the optimized valueof 1.4 fs to 1 fs and 2.5 fs respectively. These traces do not match the experimental
data.

the central 2 NIR field cycles. We obtain a 2nd order phase of D2 = −0.033 f s2 . Using
the same procedure we obtain a minimum RMS deviation for third order dispersion at
D3 = −0.007 f s3 in Fig. 3.15(b). The atomic phase of the detection gas, as well as
contributions from the EUV mirror and the Al filters, are negligible at the EUV energies

100
considered. Using the best values for the second and third order dispersions found in
this way, we construct the simulated FROG CRAB trace, shown in Fig. 3.15(e). Thisagrees very well and in detail with the experimental trace in Fig. 3.15(d). The full
simulated FROG CRAB trace is shown in Fig. 3.13(b), and compares excellently withthe experimental trace shown in Fig. 3.13(a).
1.0
8
0.8

0.8
4
0.6
0
0.4
-4

Phase (rad)EUV intensity

EUV Efield envelope

1.0

1.4fs FWHM

0.6
0.4
0.2

0.2
-8
0.0
-4

-2

0
time (fs)

2

4

0.0
-2

-1

0
time (fs)1

2

Figure 3.16: (a) Chirped EUV electric field envelope vs. time: (Dashed green) obtained
from optimized fit shown in Fig. 3.13(b); magnitude (solid blue) and phase (solid blue)
retrieved from a GP algorithm; (dotted red) transform limited pulse for comparison.
(b) (Solid blue, dashed green): EUV intensities vs. time corresponding to the chirped
pulses shown in (a); (dash-dotted green): intensity of a double pulse with the sameenvelope; (dotted black) intensity envelope of the extracted EUV field.

With the above analysis, we can now plot the correct chirped EUV electric fieldenvelope, shown in dashed green in Fig. 3.16(a). For comparison, the transform-limited
electric field envelope is also shown in dotted red. Figure 3.16(b) shows the intensity
versus time of the chirped EUV pulse (dashed green), as well as the envelope corresponding to the transform-limited center harmonic for comparison (dotted black line). Figure
3.16 shows that the attosecond bursts are broadened from their transform-limited valueof 360 attoseconds, to a chirped value of 470 attoseconds, while the total EUV radiationis contained in an overall intensity envelope of 1.4 ± 0.2 fs FWHM. This corresponds
to a single burst with two ∼ 10% sidelobes in the case of a cosine pulse. However, distinguishing a cosine from a sine pulse with two equivalent intensity bursts (dash-dotted

101
green line in Fig. 3.16(b)) is not possible (Note that the two cases could be distinguised
if a CEP stabilized NIR driving pulse was used for the temporal characterization - see
Fig. 3.23). This is because the two FROG CRAB traces are equivalent - see Fig. 3.23.
To validate the temporal FWHM EUV envelope extracted from our analysis, we also
explored the effect of varying the envelope duration in our simulated FROG CRAB
traces. We found that varying the pulse envelope also changes the widths and the shapeof the FROG CRAB sidebands, as can be seen in the simulated FROG CRAB data forvarying EUV pulse envelope in Fig. 3.15(e), (f), (g) for 1.4 fs, 1 fs and 2.5 fs respectively.
A plot of the RMS deviation between the simulated and experimental FROG CRAB
traces versus the EUV pulse duration is shown in Fig. 3.15(c). The best agreement
is found for an EUV pulse duration of 1.44 fs (FWHM), in very good agreement withthe duration of the EUV field reconstructed from the CCD spectrum for dispersionsof D2 = −0.033 f s2 and D3 = −0.007 f s3 . Furthermore we checked that including
an additional quadratic phase around each harmonic (harmonic chirp [167]) leads to aworse agreement between the data and the fit.
To validate the results of our previous analysis, we performed an independent,
unrestricted pulse retrieval using a Generalized Projections (GP) FROG CRAB algorithm. This algorithm has been adapted to our experimental situation in the same way
as was discussed above for the simulated FROG CRAB traces, to take into account photoelectron collection over a 2 − π solid angle, as well as the addition of two traces for thefundamental pulse, a cosine and minus cosine waveform, by calculating multiple FROG
CRAB traces, and comparing an appropriately averaged trace to the experimental data.
Calculated data are convolved with the photoelectron spectrometer resolution function.
The detailed implementation of this algorithm will be the subject of a forthcoming publication [152]. The resulting reconstructed FROG CRAB trace is shown in Fig. 3.13(c)and shows excellent agreement with the experimental trace. The RMS error is 1%. The
retrieved temporal electric field profile agrees quantitatively with the one extracted from102
our first analysis, and is shown in solid blue in Fig. 3.16(a). Analysis of the spectralphase of the retrieved electric field (not shown) yields second and third order dispersion
coefficients D2 = −0.032 f s2 and D3 = −0.025 f s3 in excellent agreement with our first
analysis, and in addition shows a small amount of harmonic chirp, but second (third)order terms around all harmonics are smaller than 0.1 f s2 (0.03 f s3 ), respectively. Suchsmall amounts of harmonic chirp do not measurably influence the overall EUV pulse
envelope, as confirmed by the EUV field retrieved by the GP algorithm, shown in Fig.
3.16(a), and by the analysis in [167].
Finally, we note that in earlier work [140], simulations predict a dynamicallyphase matched gated HHG regime, in which the EUV emission of one harmonic should
be localized within an optical cycle, which is consistent with our present measurements.
Numerical calculations of single-atom radiation on the other hand, predict EUV pulse
durations of 6 fs or longer for our experimental parameters, suggesting the importanceof a temporal phase matching that is reducing the EUV pulse duration in our geometry.
In conclusion, we have characterized the amplitude and phase of a complex extreme ultraviolet field with attosecond sub-structure. Using a hollow waveguide geometry we generate sub-optical-cycle pulses from relatively long 13 fs driving laser pulses.
Using the FROG CRAB pulse measurement technique, we extracted the extreme ultraviolet waveform consisting of chirped 470 attosecond bursts, spaced by ∼ 1.3 fs, within a
1.4 fs intensity envelope. We also showed that the sub-optical-cycle EUV pulses are neartransform-limited, with a relatively narrow bandwidth of ∼ 1 eV, making this source
ideal for ultrafast state-selective molecular and materials spectroscopy. In this difficult
temporal regime, where the laser fundamental cycle of 2.6 fs is comparable in duration
to the EUV pulse, we have demonstrated that the FROGCRAB technique can be successfully used to bridge the gap in EUV pulse measurement capabilities between simple
non-interferometric cross-correlation measurements, and RABBITT, which determines
the time structure of individual attosecond bursts but not the overall envelope. Finally,

103
we have shown that considerable intuition about the EUV pulse characteristics can beobtained directly from the FROGCRAB trace.

3.9

Characterizing isolated attosecond pulses from hollow-corewaveguides using multi-cycle driving pulses
This section describes a second set of experiments, in which it is shown that an

isolated pulse with duration of ≈ 200 attoseconds can result from CEP unstabilized,
high intensity ≈ 15 fs multi-cycle driving pulses coupled into a hollow-core waveguidefilled with low-pressure Argon gas.

1.0

0.8

0.8

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0.6

0.4

0.4

0.2

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0.0

30

35

40

45

photon energy (eV)50electron counts (a.u.)

photon counts (a.u.)

1.0

0.0

Figure 3.17: EUV spectrum recorded with an x-ray spectrometer (black), and corresponding photoelectron spectrum upshifted by the ionization potential (red). The
difference in spectral shape is due to EUV mirror reflectivity (which is low at the lower
photon energies).

In Figure 3.17 we show an experimental EUV spectrum using this x-ray spectrometer. The CCD spectrum shows a quasicontinuum centered around the 23rd harmonic.
We also show the corresponding unstreaked photoelectron spectrum, upshifted by theionization potential of the gas. The difference in shape is due to the mirror reflectivity of
Mo/Si EUV mirror used for focusing into the Neon detection gas jet (Mo/Si multilayer

104
mirror centered at ≈ 47 eV with a FWHM ≈ 13 eV ). This mirror therefore provides
a spectral filtering which suppresses the lower harmonics and results in a continuum

energy (eV)centered around the 25th harmonic.

30
20
10
-15

-10

-5

0
5
delay (fs)1015

Figure 3.18: Retrieval of a partial FROG CRAB trace. Experimentally, a small range(0 − 6 fs) of delay steps were taken with high temporal resolution. In order to retrieve
the EUV pulse, the data are embedded into a larger array with zeros, with ”unstreaked”
spectra (recorded without the fundamental light present) attached at large delays.

To accurately retrieve an EUV pulse, we obtained high temporal resolution datafor 2.5 laser cycles near to zero delay, with delay steps of 100 attoseconds. For sucha ”partial” FROG CRAB trace to converge, however, it is necessary to terminate thetrace with a range of ”unstreaked” spectra. Therefore we used a photoelectron spectrum
generated by the EUV radiation alone and attached it at the edges (around ±15 fs delay)of the experimental FROG CRAB trace as seen in figure 3.18. The convergence errors
are calculated only for regions where data actually exist.
Figure 3.19 shows the experimental photoelectron energy resolved two-color crosscorrelation and the FROG CRAB trace retrieved using the GP algorithm, as well as the
EUV reconstructed electric field and intensity. Here, the Gerror was 1.7%. The retrieved
single isolated attosecond pulse has a FWHM pulse duration of 210 attoseconds withnegligible (∼ 5% electric field amplitude) sidebursts, and a second-order dispersion of
0.009 f s2 . The agreement in the central energy range is good, while at high energies,

105

energy (eV)

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(c)

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0
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1

2

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(b)
EUV intensity (a.u.)

35
35

energy (eV)

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15

0

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2

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4
delay (fs)

5

(d)

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phase (radians)(a)

EUV field envelope (a.u.)

35
35

-2

6

Figure 3.19: (a) Zoom-in on the experimental photoelectron energy resolved two-color
cross-correlation shown in Fig. 3.18. (b) FROG CRAB trace retrieved using the GP
algorithm. (c) Reconstructed EUV electric field envelope and temporal phase. (d)Reconstructed EUV intensity yielding a FWHM pulse duration of 210 attoseconds.

the ponderomotive shifts are not correctly recovered using the algorithm. This is dueto the approximation of the W-dependence in Eq. (3.8) by W0 , as we will show below.
3.9.1

Direct simulations of FROG CRAB traces

In this section we employ directly simulated FROG CRAB traces. We first showthat such direct simulations can reproduce the experimental two-color cross-correlation
spectrogram shown in Figure 3.19(a). Such direct simulations allow more freedom to
explore the effect of specific pulse parameters on FROG traces, or to address specificconcerns regarding the retrieved pulse, than is possible using the automated GP re-106trieval algorithm. We then turn to a more general discussion, showing that in almost
all situations, the EUV electric field can be retrieved without carrier-envelope phasestabilization, with one important exception that we point out explicitly. Finally, weshow that in direct simulations, which in contrast to the GP algorithm do not make useof the approximation W → W0 in Eq. (3.8), the large ponderomotive upshifts seen in
the experimental trace are reproduced correctly.
To simulate FROG CRAB traces, we employed the theory described in section
3.4, and adapted it to our experimental situation, again by appropriately weighting
FROG CRAB traces obtained for different angles θ, and for CEP = 0 and CEP = π.
All simulated traces were convolved with the experimentally measured photoelectron
spectrometer resolution function, a Gaussian of 0.73 eV FWHM.
(a) CEP averaged(c) CEP=ππ(b) CEP=0

energy (eV)

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7

EUV intensity (a.u.)-1phase (radians)

EUV field envelope (a.u.)

-2

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time (fs)Figure 3.20: Simulations for (a) averaged CEP, (b) CEP = 0, (c) CEP = π, (d) retrieved
EUV field envelope and phase, (e) intensity of 200 attoseconds FWHM pulse duration.

In Fig. 3.20 we show the results of the direct simulations yielding the best fit

107
to the experimental data shown in Figure 3.19(a). In addition to the final averaged
trace (Fig. 3.20(a)), we also show the individual traces for CEP = 0 and CEP = π(Fig. 3.20(b) and (c)). The retrieved single isolated attosecond pulse has a FWHM
pulse duration of 200 ± 25 attoseconds, in good agreement with the result from thealgorithm, and a second-order dispersion of 0.005 f s2 . The error in the pulse duration
was determined by an observation of a clearly visible discrepancy between measured
and simulated FROG traces. The Fourier limited duration was 185 as. We again pointout that in these direct simulations we do not make the approximation W − > W0 in
Eq. (3.8), yielding improved agreement in the strongly streaked regions compared to
the GP algorithm (Fig. 3.19).
To generate the FROG CRAB trace above, first the gate function (i.e. the fundamental field) was obtained by optimizing agreement between simulation and full traceexperimental data taken at larger delay steps of 300 attoseconds. These data are shownin Fig. 3.21. The retrieved fundamental pulse has a FWHM pulse duration of 15f s,
Up = 0.54eV and a linear chirp of Γ2 = 0.0185f s−2 .
Secondly, the simulated FROG CRAB traces were optimized with respect to theexperimental FROG CRAB traces through a progressive fitting procedure by minimizing
the root-mean-square (RMS) deviation between the simulated and experimental FROG
CRAB traces. To this end, we include spectral phase terms describing the attochirp[167] resulting in a chirped x-ray field in time which is used as input in the simulations.
We used direct simulations to explore the question whether the measured FROG
CRAB trace might be explained by an attosecond pulse train, as opposed to a single
burst. In the case of an unchirped pulse train, already the CCD spectrum would reveal acomb of well resolved harmonics, contrary to what we observe in Figure 3.17. Therefore
we explored the possibility of a pulse train with a significant femtochirp [167, 19]. In thiscase subsequent portions of the train would generate energy-shifted harmonic combs,
such that the time-integrated measured spectrum appears as a continuum. We explored

108

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(a)

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(b)

energy (eV)

3535
3030
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-6 -4 -2 0 2 4
delay (fs)6

Figure 3.21: (a) Experimental data of complete FROG CRAB trace (b) Simulations ofexperimental data shown in (a), used to extract NIR fundamental pulse parameters.

a wide range of values for Γ2 , and find that such FROG CRAB traces are always
significantly modulated. Representative simulated data are shown in Figure 3.22. From
the amount of modulation in the calculated FROG CRAB traces, in comparison toexperiment, we can set an upper limit on the energy contained in possible side bursts,of about 5%. Although it is impossible to test for all possible chirp patterns, our results
strongly suggest that our experimental data are incompatible with a strongly chirped

109
attosecond pulse train.
A last point of concern is the following: A number of measurements so-far haveshown that the harmonic peaks in a spectrum can under certain conditions shift with the
CEP value [7, 112]. However these observations were all made with very short driving
pulses of ∼ 6 fs duration. We have calculated the phase that the electron acquires whilein the continuum (harmonic phase) using the classical electron trajectory for the shortquantum path. It is the difference in this phase between the two dominant half-cycles
contributing to radiation (see Fig. 3.25 below) that determines the spectral position ofharmonic peaks. We calculate this harmonic phase difference for different values of the
CEP, and find that for our harmonics in the plateau region the corresponding shifts ofharmonic peaks in frequency are negligible (∼ 0.2 eV) [112]. This is in agreement withearlier calculations using the saddle-point approximation that find strong effects of CEP
on high harmonic generation in the high-plateau and cutoff region only when very shortdriving pulses are used [112], whereas the amount of CEP-dependent spectral shift ofthe harmonic peaks decreases upon increasing the driving pulse duration.
We now turn to a more general discussion of the possible ambiguities in CEP
unstabilized vs. stabilized FROG CRAB traces. The left column of Figure 3.23 shows
simulated FROG CRAB traces for a single gate of CEP=0 radians, as would be measured in an experiment with CEP stabilized pulses, while the right column shows FROG
CRAB traces averaged over two gates (CEP = 0 and CEP = π radians). The figure
shows that both for isolated attosecond bursts (Fig. 3.23(a)) as well as for attosecond
pulse trains containing more than 2-3 bursts (Fig. 3.23(d)), the CEP does not need
to be stabilized for reconstruction of the temporal structure of the EUV field. Only
when working in the regime intermediate between a single isolated attosecond pulse
with small ≈ 10% intensity pre- and post pulses, (Fig. 3.23(b)) and a double pulse (Fig.
3.23(c)) there exists an ambiguity in the FROG CRAB traces. This is the intermediate
regime we studied in [154]. This ambiguity can be removed by stabilizing the CEP ofΓ2=-0.555/fs2
intensity (a.u.)40 ττe=1fs
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Experimental data

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Energy (eV)110

Γ2=+0.555/fs2

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-1

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1.5

1

1.5

1

Figure 3.22: Simulations of chirped attosecond pulse trains. Top row center: experimental data for comparison. Γ2 : femtochirp parameter in 1/f s2 . τe : envelope of thesimulated EUV pulse trains (see insets). First row: τe = 1 fs corresponds to an isolated
attosecond pulse with two, 10−3 intensity side bursts. τe = 1.5 fs: two, 5% intensityside bursts. All simulated traces with τe > 1.5 fs show significantly more spectral modulation than the experimental data. Simulated traces have been convoluted with theexperimental photoelectron spectrometer resolution function.

111
the fundamental laser pulse. While the position of the burst(s) underneath the envelope
cannot be determined without CEP stabilization, the attosecond pulse structure of theindividual attosecond bursts, as well as the overall intensity envelope, can be retrieved

35

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(d)

20
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-1

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-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5

time (fs)225-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5

time (fs)230-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5

time (fs)2

5-2

energy (eV)

0.4

5

5

energy (eV)-23535 (b)

35

0.6

5
-2

EUV intensity (a.u.)

5

Input pulse

CEP averaged

EUV intensity (a.u.)3535 (a) CEP=0

EUV intensity (a.u.)energy (eV)[154].

0.6

0.4

0.2

0.0

-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5

time (fs)Figure 3.23: Simulations of FROG CRAB traces for different number of EUV bursts.
Left column: CEP stabilized traces; middle column: CEP unstabilized traces obtainedby averaging over CEP 0 and π; right column: EUV intensity of input pulses.

112
Lastly, we compare the reconstructed traces using the GP algorithm (Fig. 3.24(b)) which does not contain the dependence on final photoelectron kinetic energy, withthe progressive fitting simulation code (Fig. 3.24 (c)) which contains the final photoelectron kinetic energy dependence. Visually it is obvious that the simulation code achieves
a better agreement with the experimental trace Fig. 3.24 (a) than the GP algorithmwith the W → W0 approximation. Also, in the simplified geometry (2◦ photoelectron
detection angle and CEP stabilized) of [141] there is a systematic error between experimental and reconstructed trace due to this neglected energy dependency, which leads toponderomotive shifts that are too weak at high photoelectron energies and too strong at
low photoelectron energies. It was found [101] that this energy dependence is only negligible if the bandwidth of the attosecond pulse is small compared to the center energy,
which is not fulfilled in [141] and the data presented here.
Thus it would be desirable that reconstruction algorithms such as the GP and
PCGP [81] include the energy dependence in future implementations.
40

energy (eV)

3535

(a)

(b)

(c)

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2020
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2 -2

-1 0
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delay (fs)

2 -2

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Figure 3.24: Comparison of (a) experimental data, (b) GP algorithm, and (c) direct
simulations of FROG CRAB traces using optimized EUV pulse parameters.

113
3.9.2

Interpretation of single attosecond pulse generation mechanism

In this section we give a qualitative explanation for the main experimental result described in section 3.9, which demonstrates the generation of a single isolated
attosecond pulse from a ≈ 15 fs, CEP unstabilized driving pulse. In essence, under our
experimental conditions, efficient EUV generation is only possible on the leading edgeof the driving pulse, before the coherence length gets too short due to the rapidly risingtime-dependent ionization caused by the high-intensity driving pulse.
On the leading edge of a femtosecond pulse, every consecutive half-cycle has ahigher instantaneous intensity, so that in each half-cycle a new spectral range of EUV
radiation with a higher cutoff than in the previous half-cycle can be generated, seeFig. 3.25 (a). This has been described in [60, 22, 122] and recently named “half-cycle
cutoffs”. If now from one half-cycle to the next, high harmonic generation can besuppressed, then the last half-cycle produces a spectral continuum corresponding to the
bandwidth of radiation that was not accessed in the previous half-cycle. If lower-energy
emission produced in more than one half-cycle is spectrally filtered out, a single isolated
attosecond pulse remains.
In our case, a dynamic phase mismatch between driving laser and EUV radiation
provides the mechanism that rapidly shuts off EUV generation. The phase mismatch is
given by∆k(t) = q · klaser (t) − kq

(3.22)

where kq is the wave vector of the q’th harmonic, and the fundamental laser wave
vector klaser (t) is given by [135]klaser (t) ≈ 2π/λ +

2πN (1 − η(t))δ(λ)
u2 λ− N η(t)re λ − nm 2λ
4πa(3.23)

Here, N is the total gas density (neutral gas plus plasma), η(t) is the time-

114

cutoff (harmonic order)

(a)

60
50
40
30
20
10

phase mismatch (1/m)

(b)

5000
0
-5000

-10000-15000-20000-25000-20-10

0time (fs)10

20

Figure 3.25: (a) EUV cutoff harmonic as a function of time, determined from instantaneous intensity. (b) phase mismatch [135, 54] for the 25th harmonic versus time forstraight fiber (red), effect of employing a QPM fiber for same pulse parameters (blue).
Horizontal dashed lines: region of experimentally generated EUV spectrum. Vertical dashed lines: guides to the eye highlighting the half-cycles in which efficient EUV
generation is possible: Earlier, the instantaneous intensity is too low to generate theexperimental spectrum (lower harmonics are absorbed in the generating Argon gas, andnot reflected by EUV mirror). Later, large phase mismatch prevents coherent build-up
of EUV radiation.

dependent ionization fraction, δ(λ) describes the dispersive characteristics of the atom,
re is the classical electron radius, a is the waveguide radius, and unm is the mth rootof the (n − 1)th Bessel function of the first kind and depends on the transverse modes
coupled into the waveguide. The EUV radiation is not significantly affected by any of
the three dispersion contributions, and its wave vector kq in Eq. 3.22 is only slightly

115
modified from its vacuum value. In our low-pressure Argon, as shown in Fig. 3.25(b), initially the phase mismatch is small, and EUV generation can occur. As soon as
the intensity starts to increase rapidly on the leading edge of the pulse, it generates avery rapidly increasing plasma density. This growing plasma contribution sweeps thephase mismatch through zero and then to large negative values, such that high harmonic
generation is suppressed for all later half-cycles.
The spectral filtering of lower harmonics (produced in several of the early halfcycles), required to isolate a single attosecond pulse, is achieved by the Mo/Si EUV
mirror focusing the radiation into the detection gas jet. In addition, low harmonics are
already strongly absorbed in the Argon gas. Note that there could also be some spatial
filtering by the small EUV mirror [48], similarly as in the experiment of Ref. [63].
To further support the ionization gating mechanism we performed propagation
simulations for the driving laser with the purpose of finding the best pressure and laser
peak intensity parameters for ensuring phase matching at a specific time window. The
propagation equation we used is a one dimensional version of the extreme-nonlinear
optics propagation equation developed by Geissler et al.[53] modified to include neutral
gas dispersion and waveguide dispersion. The ionization of the medium was calculatedusing an ADK-based model[145]. As the generated high harmonics propagate with
virtually no dispersion they can be considered to propagate at the speed of light. Because
the propagation equation is calculated in a frame moving at the speed of light thedegree of overlap of the laser pulse as it propagates in the medium with the one at
the beginning of the medium is a measure for the temporal phase mismatch: at thosetimes where there is perfect overlap the generation of the high harmonics would becompletely phase matched. A similar approach was used to explain the generation of
sub-optical cycle, CEP insensitive, EUV pulses [140]. To find the best parameters forour case we defined a phase-matching-criterion: the temporal overlap in the desired
time-window divided by the temporal overlap outside this time window, integrated over116
the propagation coordinate, should be as large as possible. The time window was definedas the interval between the moment the laser intensity is high enough for generationof the 21st harmonic to the moment it is high enough for the generation of the 29th
harmonic (as indicated in Fig. 3.25). Plots of this phase-matching-criterion are shownin Fig. 3.26 a-b for two different values of CEP. Warmer colors correspond to better
phase-matching-criterion. We note that the best pressure is almost the same for thetwo different CEP values while the best peak intensity changes by ∼ 10% indicating
only a small sensitivity to the CEP value. The estimated best peak intensity is different
by only ten percent from the one estimated in the experiment while the estimated best
pressure is about half of that estimated in the experiment which at such low pressures(∼ 10 Torr) could be within the experimental estimation error. In Fig. 3.26 c-d thelaser pulse at the end of the medium overlapped over the pulse at the beginning of themedium is shown for the two CEP cases for the best parameter values. As can be seen
the overlap is optimized at the desired time window.
The numerical results of Fig. 3.26 indicate a blue-shift in the spectrum. This does
not agree with measurements of the spectrum before and after the fiber, which showed
only a small amount of reshaping. The reason for this discrepancy is that we usedhere one-dimensional simulations relevant only to the center of the radial laser intensity
profile where the nonlinear conversion process is most efficient. Taking into accountthe radial intensity distribution combined with the low pressure within the fiber would
wash out this blue-shift in a spectral measurement. For example, simulations we did
indicate that once the field amplitude reduces to 60% of its peak value the spectral blue
shift is only around 10% of the spectrum FWHM. In addition, the simulation assumed
the same pressure conditions all along the fiber, while in the experiment a pressure
gradient towards the end of the fiber could also reduce the spectral distortion. While
the radial averaging reduces the spectral distortion, it does not destroy the dynamic
phase-matching mechanism: the length scale needed for this mechanism is on the order

117

a

b

c

d

Figure 3.26: Phase matching conditions for ionization gating. Phase-matching-criterion
for the time window in which the 21st-29th harmonics are first generated as a functionof the laser peak intensity and gas pressure for (a) CEP = π/2 (b) CEP = 0. Warmer
colors represent better phase matching. The corresponding temporal overlap of the laser
pulse at the end of the medium (red) over the pulse at the beginning of the medium(blue) is shown in (c) and (d).

of several coherence lengths (a few mm).

3.9.3

Conclusion and Outlook

In Section 3.8 [154] we reported a technically simplified method for generating
sub-optical cycle EUV radiation, consisting of either a single attosecond burst with asmall pre-and post-pulse, or a double attosecond burst. The radiation was spectrally
narrow (∼ 1 eV) and energy-tunable simply by changing pressure and intensity in thehollow waveguide, making it a very useful tool for future investigations of state-selective
molecular and materials dynamics.

118
In the other EUV regime studied [152], we have shown experimentally that it
is possible to generate a single isolated attosecond pulse with ≈ 15 fs driving pulses,
by using dynamic phase-matching in a noble-gas filled hollow-core waveguide combinedwith spectral filtering.
To temporally characterize the attosecond pulses, we have used photoelectronenergy resolved two-color cross-correlation and both a GP algorithm and direct simulations of the FROG CRAB traces. These were both extended from the conventional,
angularly restricted photoelectron detection and CEP stabilized fundamental pulses, toa more efficient 2 − π detection scheme and CEP unstabilized pulses. Both reconstruction methods agree very well on the temporal structure of the EUV pulse, finding anear-transform limited isolated EUV burst of ≈ 200 attoseconds FWHM (Section 3.9).
The generation mechanism in this case is limited to the energy range we observed: as
the pressure in the waveguide is increased, the quasicontinuous spectrum evolves towards separated harmonics. Adjustment of other parameters such as e.g. the pulse
energy may make it possible to extend this study to the generation of attosecond pulses
with tunable center wavelength. In addition, the use of different generation gases in thehollow-core waveguide and spectral filtering with EUV mirrors may allow for tuning.
While the position of individual harmonics is only weakly CEP dependent in our regime,
it remains to be studied if tunability of the spectral envelope (i.e. center energy) could
be achieved in a hollow-core waveguide by changing the CEP of the driving pulse, as
was shown for a 2 mm gas cell [122].
We believe that macroscopic effects [49, 3] are an important parameter for single
attosecond pulse generation and can be used to generate tunable isolated attosecond
pulses from multi-cycle driving laser pulses. One possible route to change the center
wavelength of the attosecond pulse would be to employ quasi-phase-matching (QPM)
methods [23]. In QPM one employs e.g. periodically modulated fibers to add a constantoffset to the phase mismatch. This offset is tunable by changing the modulation period,

119
and allows to shift the phase-matching window in time (see figure 3.25), and thereby one
could phase-match half-cycles of different instantaneous intensities. This could createa very short temporal window closer to the maximum intensity of the laser pulse andtherefore could lead to the generation of a continuum at higher energies.
Alternatively, the use of spatiotemporal shaped driving pulses for isolated attosecond pulse generation could be investigated [168, 49]. This technique produces
fundamental pulses with a fast rising edge, which should be well suited for generating
isolated attosecond pulses.
Finally we note that the spatial mode profile of the driving laser in the hollowcore waveguide is a very important parameter in determining the spectral and temporal
structure of the generated EUV radiation, and that therefore it is worth studying theseparate contributions from the spatial mode profile and temporal profile of the fundamental pulse in detail [172].

Chapter 4
Combining femtosecond-EUV pulses with the COLTRIMS technique
as a novel spectroscopy method in molecular physics

This chapter contains material published in [156].

4.1

Introduction
While the previous chapters dealt with the generation and temporal characteriza-tion of high harmonics, in this chapter we turn our attention to applications of table-top
extreme ultraviolet pulse sources.
The unique properties of EUV radiation, such as good coherence [12], short wavelength (allowing for imaging with high spatial resolution) [138], femtosecond and evenattosecond time resolution, high brightness, high repetition rate, tunability, compactness and the temporal synchronization with the NIR driving pulse, make it a uniquesource for time-resolved pump-probe spectroscopy. Recently, pump-probe experiments
using high harmonic radiation have led to the tomographic reconstruction of the highest occupied molecular orbital of N2 [72] and proton dynamics in molecules as well as
structural rearrangement after removal of an electron was probed [6]. The excellent
time resolution of high harmonic radiation also makes it an exquisite source to study
highly excited molecular states, which have been difficult to study so far. Excited states
can either be emerging from inner valence shell excitations or outer valence excitations
that can occur in combination with shakeup processes (where one photon excites one

121electron into the continuum and a second electron into a higher lying state). Nearinfrared femtosecond pulses can also be used in combination with EUV radiation to
perform pump-probe experiments. NIR pulses are used e.g. for the study of strong-field
phenomena [120] or to create aligned molecular samples[146].
Combining the exquisite time resolution obtained with femtosecond near-infrared
pulses or EUV pulses, with sensitive detection techniques such as a COLTRIMS (COLd
Target Recoil Ion Momentum Spectroscopy) apparatus (which provides single-particle
sensitivity, coincidence capabilities, and 3D momentum imaging, as presented below),creates a very powerful tool for molecular physics. New information can be gained about
unknown excited states, arising from inner- or outer valence shell excitation, as was e.g.
demonstrated in [51], where the potential curve of a shake-up state was determinedby means of a known Coulomb explosion channel. Very fast dynamics of inner-valence
excitations such as from an Auger decay [106, 37] or other autoionization processes canbe time-resolved. The coincidence detection of electrons and ions and their respectively
complete momenta allows for the measurement of molecular-frame photoelectron angular distributions, which are very complex and reveal detailed information e.g. about
theoretically challenging correlated multi-electron dynamics in molecules [30].
In the following I will describe a pump probe experiment using few femtosecond EUV pulses and a COLTRIMS apparatus to answer a very basic open questionin molecular physics: What is the orientational dependence of molecular photoionization (see artist’s impression in Fig. 4.1)? To this end, first an aligned sample ofgas-phase molecules must be created. In our experiment, molecules are impulsivelyaligned by means of intense femtosecond pump pulses. The excited molecular rotational
wavepacket experiences revivals even a long time after the pump pulse has left. During
such revivals the molecular axes change their orientation from parallel to perpendicular with respect to the polarization of the pump pulse within a few 100 femtoseconds.
Therefore photoionization by femtosecond EUV pulses with variable delay during a re-122

Figure 4.1: Artist’s impression of molecular photoionization. Credit: Greg Kuebler

vival is equivalent to photoionization of molecules with different orientation. The highenergy (here ∼ 42 eV) of the probe pulses leads to the ionization of molecules into nondissociating and dissociating channels, whereby for both channels the angle-dependent
probability for single-photon photoionization could be measured. With this novel spectroscopic method the orientational dependence of single-photon photoionization of N2
and CO2 into non-dissociating channels, as well as a long-lived state of CO2 could bemeasured for the first time.
In the following I will therefore introduce the COLTRIMS technique (Sections
4.2 and 4.3), give an introduction to molecular alignment (Section 4.4), and present ourexperimental results on the angular dependence of photoionization (Section 4.5).

4.2

The COLTRIMS technique
The COLTRIMS technique [34, 39] permits the coincidence detection and recon-

struction of the full 3D momentum vectors of all charged particles (electrons and ions)which result from one individual molecular reaction. In the simplest case, the reaction

123
could be the fragmentation of an individual molecule under irradiation with ultrashortintense laser pulses or EUV pulses, or collision with an energetic particle. Importantly,
the COLTRIMS technique has multi-hit, coincidence capability and reconstructs the full
3D momenta. In contrast, e.g. the velocity map imaging (VMI) technique only records
a 2D image and reconstructs the full momentum by an inverse Abel transform for systems with cylindrical symmetry [40], limiting studies to a fraction of systems containing
cylindrical symmetry. A disadvantage of the COLTRIMS technique, or any techniquemeasuring coincidences, is that the event rate of generated electron-ion pairs per laser
pulse needs to be much smaller than one to avoid false coincidences. COLTRIMS wasdeveloped in Frankfurt (Germany) by Horst Schmidt-Böcking and coworkers startingin the ’70s and has been commercialized in the ’90s by Roentdek [34, 39]. It has been
applied to systems in the gas phase as well as to surfaces.

Figure 4.2: The COLTRIMS setup. A light source is focused onto a gas jet in the centerof the apparatus. The ion (blue trajectory) and electron (red trajectory) are guided
to opposite time-and position sensitive detectors (red, blue) by electric and magnetic
fields. Taken from [1].

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Figure 4.2 shows a schematic of the COLTRIMS setup: A light source is focused
into a supersonically cooled gas jet where it causes a single ionization event. The
ion (blue trajectory) and electron (red trajectory) are guided to opposite time-and
position sensitive detectors by electric and magnetic fields, where they are detected incoincidence. All electrons and ions emitted into the full 4 − π solid angle are collected.
From time and position of the hit, the full three-dimensional initial momentum can bereconstructed, as will be described below.
In the following we give a short overview of the physical components of a COLTRIMS
apparatus, the electronics used for reading out the detectors, available software for acquiring and analyzing the data and the setup of pump/probe beam lines.

4.3

Components of a COLTRIMS apparatus

4.3.1

Supersonic gas jet and COLTRIMS chamber

For gas-phase experiments, the target source is provided by a supersonic jet,shown in Fig. 4.3. This source provides a narrow initial translational velocity spreadof target molecules as required for best spectroscopic resolution. In addition, internal
degrees of freedom, i.e. rotations and vibrations, are cooled to have easier interpretable
spectra. Lastly, it allows a small interaction volume with the laser beam - this isrequired, as the COLTRIMS does not provide focusing of particles generated at different
positions transverse to the axis toward the detectors.
The COLTRIMS apparatus is built up around this gas jet. It consists of threemain vacuum chambers at different operating pressures: a gas jet chamber, a detector
chamber and a catcher. A steel tubing (1/4 inch) delivers the gas through an in-line
filter to a 30 micron diameter nozzle, which is situated inside the gas jet chamber. The
gas line tubing is backed by ∼ 1 atmosphere of pressure, whereas the gas jet chamberon the other side of the nozzle is kept at ∼ 10−4 Torr by means of a 2000 l/s MAG

125

Figure 4.3: Setup of the supersonic gas jet. (a) green: the skimmer, located above
the nozzle in which supersonic expansion and cooling occurs, transmits the central,transversely cold region of the jet, to the interaction region above. (b) gas delivery
setup, and catcher (top). From [39].

turbo pump from Leybold backed by a rotary vane pump (Leybold HV Chemical (Trivac
D65BCS), 75 m3 /hour). The pressure drop through the nozzle produces a supersonic
expansion of the gas which cools it (This explains the ”COLd Target” in the acronym
COLTRIMS). Supersonic expansion happens even for expansion into a vacuum of 10−4
mbar. The position of the nozzle is adjustable via a 3-axis manipulator. The gas jet
is then skimmed by a 300 micron diameter skimmer (13 mm downstream from thenozzle [39]) to further reduce its temperature and size. Thereby one selects the ”zoneof silence” (see Figure 4.4) which is the region where the gas reaches supersonic speed

vjet = αwhere α =p
kB T0 /m

(4.1)

√
√
7 for diatomic gases and 5 for atoms and T0 is the temperature of

the gas before the expansion. The gas jet exits through the skimmer into the detection
chamber and reaches a diameter of 6 mm and internal temperature generally on the orderof 100 mK (Tint = 52 ST02 where S is the speed ratio depending on the gas, temperature
T0 as well as nozzle diameter and the stagnation pressure p0 , see Fig. 4.4.).

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Figure 4.4: Schematic of a supersonic gas jet. The gas expands from the backing
pressure region (left) into the supersonic zone of silence. The Mach number is the ratioof gas speed to the speed of sound. Adapted from [107].

The size of the gas jet limits the momentum resolution along the x-axis, which
limits the total momentum resolution. The uncertainties of momenta along the y- andz- axes are smaller as they are given by the diameter of the EUV and NIR laser beams
intersecting with the gas jet. The pressure in the detector chamber reaches 3 × 10−9Torr without gas and ∼ 10−7 Torr with gas [39]. To maintain the high vacuum insidethe detection chamber a catcher for the gas jet is brought as close as possible to theinteraction region (limited by the dimensions of the electrodes that create an electricfield around the interaction region). The catcher has a 250 l/s turbo pump by Varian
attached to it, backed by a TriScroll 600 pump from Varian (pumping speed 30m3 /hr).

4.3.2

Electric and magnetic fields

Here I describe the electric and magnetic fields that guide the charged particles
from the interaction region to the detectors. The electrons and ions generated in theinteraction region are separated by a homogeneous electric field along the spectrometer
axis, such that they are accelerated to opposite detectors (HEX-detector for electrons,

20
0
-20
-60

-40

DLDy (mm)

40

60

127

-60

-40

0
-20
20
DLDx (mm)4060Figure 4.5: Ionization events from gas jet (intense spot) and background gas (diffuseband). The vertical offset, together with the time of flight, gives the gas jet velocity(4.1).

DLD-detector for ions, see below). This electric field is generated by applying a voltage
over a chain consisting of alternating resistors (100 kOhm) and Copper square electrodes (41 electrodes with a center hole of 13 cm diameter spaced by 0.5 cm). The
homogeneous electric field is properly terminated by transmission meshes (each about
80% grid transmission efficiency) in front of the detectors. While the ions only passthrough an acceleration region of length ∼ 11.6 cm, the electrons traverse in addition
to the acceleration region a field free drift region generated by two transmission meshes
at the same potential. The drift region is twice as long (24.2 cm) as the acceleration
region (12.1 cm). This design makes sure that electrons that are generated at slightly
different positions in the interaction volume along the spectrometer axis arrive at thedetector at the same time (Wiley McLaren time-lag focusing [171]).

128
In order to confine electron detection to the size of even the largest commerciallyavailable detectors, a magnetic field is required. This contrasts with the ions, for thefollowing reason: Assume only an electric field E guides the electrons. The detector
needs to be larger than a typical hit position xhit = vini · T OF . Inserting the time ofq√
2mLT OF
2 gives x
flight T OF found from LT OF = 21 qETOF=v∼ vini m. Now
ini
hit
m
qE
compare the hit position on the detector xhit for electrons and ions: Using momentum
p
e
ion
e =m
conservation in the ionization process me vinimion /me xion
ion vini one gets xhit =
hit .
p
√
This means that electrons would require a detector mion /me ∼ 1836 ∼ 40 times
larger than that required for the lightest ion!
An additional homogeneous magnetic field along the spectrometer axis is therefore
used to confine electrons with large perpendicular momentum mvperp to a cyclotron
radius of R = mvperp /(qB). The strength of the B field is chosen to fill a good fractionof the electron detector. This magnetic field in principle affects the ions too, but thecyclotron period for ions Tcyc = 2πmion /(qB) is in general much larger than the iontime of flight, so that the ion image is hardly affected.
The magnetic field is generated by two identical coated copper coils (10 gaugesquare copper wire with 100 turns) which are separated by a distance equal to the radiusof the coils (Helmholtz geometry). Two coils with smaller radius are added at the far
ends to extend the region of the homogenous magnetic field. In addition to these large
coils creating a magnetic field along the z-axis, a set of 4 additional coils made out of 37
turns of computer cable are used to shield the COLTRIMS apparatus from the earth’s
magnetic field (∼ 0.32 Gauss) and other laboratory generated magnetic fields (one pairof coils along the x-axis and one pair along the y-axis).
The experimentally chosen electric field strengths (typically several 100’s V/m)
and magnetic field strengths (typically 5 − 10 Gauss) vary depending on the ions andelectrons investigated in a reaction. As the electric field strength is the dominant parameter affecting the ions, its strength is generally adjusted such that a significant fraction

129of the ion detector is covered by the ion hits of interest. The magnetic field is then chosen such that electron hits fill the electron detector. However, one has to avoid electron
flight times corresponding to integer multiples of the cyclotron period when all electron
trajectories return to the initial transverse position irrespective of their momentum this would severely degrade momentum resolution (see below). In general one needs tofind a compromise between the spread of arrival times of the electrons with different
kinetic energies (Does one want to look at only one electron or detect a second electron
in coincidence?). In addition one wants to assure that all generated ions and electrons
in the reaction are hitting the detector.
4.3.3
4.3.3.1

Electron and ion trajectories
Equations of motion for ions

In the following we will give the equations of motion for ions and electrons in anelectric field E and a magnetic field B, both parallel along the z-axis. We will see that
we can determine the complete initial momentum vector for any charged particle, by
measuring its time of flight and its coordinates on a two dimensional position detector.
Solving the equations of motion for ions, we find that the initial momentum components
can be measured from the hit position (x(T OF ), y(T OF )) on the detector as well as
the time of flight (TOF) from the gas jet to the detector:x(T OF ) − x(0)
T OF

(4.2)

y(T OF ) − y(0)− m · vjet
T OF

(4.3)

m · L q · E · T OF
−
T OF
2

(4.4)

px = m ·py = m ·pz =where m is the mass of the fragment, and x(0) is the x-position of the gas jet.
For the initial momentum in y-direction we have to subtract the upward velocity of the

130supersonic gas jet vjet . For pz we have L which is the length from gas jet to detector
and q the electric charge of the ion.

4.3.3.2

Equations of motion for electrons

For the electrons we also have to consider the B-field:
Starting with the equations of motion for x and y for the electronsmẍ = −eẏB(4.5)

mÿ = +eẋB(4.6)

We can then define a new variable ϕ̇ = ẋ + iẏ. Choosing the correct Ansatz
ϕ̇ = A · exp iωt the new variable ϕ̇ and initial condition ϕ̇(0) = A = ẋ(0) + iẏ(0), we
can integrate ϕ̇. This gives us the equations for the position hits on the detector, x andy, which can finally be solved for the initial momentum components px and py of theelectron:px = mb·x−a·ya2 + b2(4.7)

py = ma·x+b·ya2 + b2(4.8)

sin(ωt)where a = cos(ωt)−1
with ω = eBωm the cyclotron angular frequency and b =ωand t is the time-of-flight.
Equations (4.7) and (4.8) show that the transverse momenta cannot be determined under the condition when a2 + b2 = 0. This is the case when the electron TOF isan integer i number of full cyclotron orbits (ω · T OF = i · 2π) and all electrons returnto their initial transverse position independent of their initial momentum, leading to acharacteristic ”fish” structure in the x-position/y-position vs. TOF image (see Figure4.6). It is important to adjust the magnetic field strength B such that these ”nodes”
in the electron trajectories occur outside the range of electron momenta accessed in agiven experiment.

0
-60

-40

-20

Yrot (mm)

20

40

60

131

80

200
140
TOFe (ns)260

Figure 4.6: Magnetic field calibration using ”fish” images (transverse electron hit position Yrot versus time of flight). The time between the two nodes gives the cyclotron
period and hence the magnetic field strength.

To calculate the initial momentum component pz along the spectrometer axis
we have to consider the motion in the electric field along the acceleration region andsubsequent motion in the drift region. Solving the equation of motion in the acceleration
region gives us:
m · La = pinitial· T OFa − eEz

T OFa22(4.9)

with La the acceleration region and T OFa the time of flight in the acceleration
region.
The equation of motion in the drift region gives us:
m · (La + Ldrif t ) = m · La + (pinitial− e E T OFa · (T OF − T OFa )z(4.10)

132
where Ldrif t is the drift region and TOF is the measured total time-of-flight.
With the two above equations we can solve for the two unknowns pinitial
and T OFa .
z
4.3.4

Detectors and electronics

Figure 4.7: The DLD detector, taken from [57]. On top is a multichannel plate which
amplifies an incident electron to a charge cloud that exits on the back side. The positionof this cloud is recorded by a two-dimensional delay-line anode (one vertical and one
horizontal wire wound into a grid). Position-sensitivity is achieved by measuring thetime difference of two signals traveling on the delay line in opposite directions of thevertical and horizontal wire, respectively.

The core pieces of a COLTRIMS apparatus are the time- and position- sensitive detectors for the electron and ion fragments. The detector used for the ions was
a 2-dimensional delay-line-detector including microchannel plates (MCPs in Chevron
configuration) with an active area of 12 cm (DLD120 Roentdek), shown in Fig. 4.7.
The detection principle is as follows: First an ion or an electron hits the microchannel
plates (MCP) (MCP front biases can be varied from −4 kV to +1 kV). Along the mi-133crochannels this hit leads to a cascade of secondary electron emission. This amplified
electron pulse gives the measured time-of-flight signal. Behind the MCP plates are thedelay-line anodes which measure the position of the hit: The charge pulse created by
the electron in the microchannel plate exits the back side of the MCP, where two wires
are wound into a grid (see Fig. 4.7). Each wire provides spatial information in one
dimension. The position of an electron hit is measured from the time difference of thecharge pulses traveling to opposite ends of the wire 1 . In practice a pair of wires is used
– a signal and a reference wire – where the signal wire is at a slightly higher potentialof +40 V and therefore carries the electron pulse. The signal and reference wire createa transmission line that has the advantage of minimizing losses and dispersion of thecurrent pulse, and is usually used for the transmission of high frequency pulses. It also
allows to amplify only the differential signal and therefore to reject any noise pickedup along the way on both wires. The signals are coupled out over an RC element andare then amplified. Even though the distance between adjacent wire windings is ∼ 1
mm, the position resolution of the detectors is < 100 microns. This is because one
can determine the center of charge of the electron cloud hitting the anode grid more
precisely than the wire spacing. The spatial resolution is therefore really limited by theinteraction volume defined by the gas jet and the laser beam widths. The count rate ofdetector can be 1 MHz but is limited by the attached electronics (see below). The time
resolution is ∼ 500 picoseconds.
The electrons are detected with a 2-dimensional Hexanode detector (HEX120)
with the same properties as the ion detector, except that it includes a third layer of delayline wire offering redundant information which can be useful in cases where multiple
electrons with similar time of flights or positions are detected in coincidence. This HEX
detector is shown in Fig. 4.8.
The signals from the MCPs and delay-line-anodes are amplified and then constant1

Note that the wires traveling in the y-direction determine the x-position of the hit.

134

Figure 4.8: The HEX detector, taken from [57]. The principle is the same as for the
DLD detector, with the exception of a third delay line offering redundant information
for improved multi-hit performance.

fraction discriminators are used to create NIM (Nuclear Instrumentation Module) pulses(ATR19 Roentdek). A constant fraction discriminator takes input pulses and converts
them independently of their peak height fluctuations into pulses that contain the accurate timing information of the input pulses, i.e. it creates a pulse output always at thesame fraction of the input pulse. It also allows to set a threshold for the input signals andthe created output NIM pulse has a precise shape and height of −0.9 Volts. The NIM
signals are then fed into two synchronized time-to-digital converter boards (T DC8P CI2
Roentdek). Each TDC board has 8 channels (based on the LeCroy M T D133B chip),
can acquire data for a 32µs range with 500 ps resolution (16-bit dynamic range). It
has multi-hit capabilities up to 16 hits with a multi-hit dead time of ∼ 10 ns. Data

135
Table 4.1: Typical potential settings for COLTRIMS electric field.
DLD
Signal/Reference
180 V
HEX
Mesh
-200 V

Holder
100 V

MCP back
0V

MCP front-2100 V

Mesh
-450 VMCP front-50 V

MCP back
2150 V

Holder2250 V

Signal/Referece
2330 Vacquisition speed can be 25 kHz for 1 hit per channel, but decreases for more hits.

4.3.5

Data analysis

For acquisition and analysis the CoboldPC software from Roentdek is used. A
data acquisition program written in C++ and a command file are used for data acquisition. All events are saved in list-mode format. In a list-mode file each individual
event is stored with its position and timing information, so that the full information isavailable for re-analysis at any time.
In addition the list-mode file can be loaded later using a data analysis program
also written in C++ with which it is possible to reanalyze the data using filters on eventsand extracting momenta and energy information as well as coincidence information.

4.3.6

Coincidence detection

For coincidence detection of several charged fragments the question one needs
to pose is what event rate can one afford to ensure true coincidences. Therefore one
typically uses the system in a mode, where ¿ 1 event per pulse is detected. Generally
speaking, one needs to determine the final number of events per pulse in the gas jet, andmake sure that two of these events per pulse occur with a significantly lower probability
than one event. As a rule of thumb, by making sure the event of interest is happening
only every tenth laser pulse, this also ensures that the ratio of double events to single

136
events is only about 10%. In general this has not yet been of much concern in our
setup, as cross sections (typically on the order of 10−19 cm2 ), gas jet density (on theorder of 1011 /cm3 ) and photon flux in the COLTRIMS target region (Np ∼ 3 · 106
photons per pulse at ∼ 45 eV at the gas target) are not very high. Event probabilities
are nLσNp ∼ 1% per pulse for a L ∼ 3 mm gas jet.
4.3.7

COLTRIMS detection efficiency and optics efficiency

Not all events produced in the gas jet are also detected. The number of ionsand electrons detected are strongly reduced by the use of meshes (∼ 80% transmission
efficiency) in the COLTRIMS detection setup (These meshes provide a more homogenous
electric field). Two of those meshes are at the beginning and end of the drift region for
the electrons and one mesh is used in front of the ion detector. In addition the efficiencyof the MCP and delay line anode is only ∼ 30%.
The EUV photon flux (∼ 108 photons per pulse out of the generation waveguide)
is also reduced by the usage of 2 EUV mirrors and an Aluminum filter. The Aluminum
filter is used to reflect the NIR driving pulses. The COLTRIMS beamline consists of
two Mo/Si (molybdenum-silicon) EUV multilayer mirrors in a z-fold configuration witha reflectivity of 20 − 25% at ∼ 43 eV and an Aluminum filter of 200 nm thickness witha transmission of ∼ 64% at ∼ 43 eV (0.22 · 0.22 · 0.64 = 0.03). This reduces the EUV
photon flux to ∼ 3 · 106 photons per pulse.

4.4

Molecular alignment methods
Here I give an introduction to molecular alignment, as this experimental tech-nique is used later in this thesis to determine the angle-dependent photoionization ofmolecules. There exist two distinct regimes of molecular alignment: The first regime,
referred to as ”adiabatic alignment” [114, 136], requires a very strong static electricfield (10’s of kV/cm) or a long laser pulse (picosecond to nanosecond), that slowly turns

137
on and off compared to the molecular rotational period, and aligns the molecular axes
along the electric field/ laser polarization by exerting a torque on the permanent dipole
d or the induced dipole d = α E, where α is the polarizability tensor. The interactionenergy is given by:
V =−

d·E
B

(4.11)

here B is the rotational constant, E the electric field and d the dipole moment. A review
can be found in [146], where results of adiabatic alignment of iodine (using a noble gas
as buffer gas to further lower the rotational temperature) with an alignment cosine (seebelow) of 0.85 were demonstrated. The highest degree of alignment (< cos2 Θ >= 0.92)
using 9-nanosecond long pulses has been shown in iodobenzene by Kumarappan [88].

Figure 4.9: Definition of molecular polarizabilities α|| along and α⊥ perpendicular to
the molecular axis. The alignment field E torques the molecule towards the field axis.

The second regime is referred to as ”non-adiabatic alignment”. It employs ashort laser pulse to impulsively excite a coherent rotational wave packet, which undergoes periodic dephasing and rephasing (revivals) and transiently aligns the molecules.
These field-free alignment revival structures allow probing the aligned molecules while
unperturbed by external fields and therefore are attractive for studying the interaction

138
between non-perturbed free molecules and photons. This is the regime which we use
below for the alignment of molecules with femtosecond pulses.

4.4.1

Field free (nonadiabatic) molecular alignment

Alignment
femtosecond
IR pulse

0
isotropic
sampledelay τEalignzθtorqueMolecular axes distributionA(θ ,τ )…

cos 2 (θ ) = ∫ sin(θ ) cos 2 (θ ) A(θ ,τ ) dθ
0.4
0.36
0.32
0.28
0.24

0

10

20
30
delay [ps]

40

50

z

Measurements
versus delay areequivalent toprobing molecules
at different angles!

z

θ
y

x
alignedantialigned

Figure 4.10: Molecular alignment: A femtosecond laser pulse impulsively torques themolecular axes towards its polarization direction. The molecular axes distributionA(θ, τ ) experiences periodic revivals, as demonstrated by peaks and dips in the alignment cosine < cos2 (θ) >. During the half-revival around 21 ps for CO2 the axes
distribution changes from aligned to antialigned.

139
For the experiments described here we use nonadiabatic alignment to align themolecular sample. In this case the employed alignment pulses are much shorter than
the rotational period of the studied molecules. For example for the molecules CO2 andN2 the full revivals occur for ∼ 42.6 ps and ∼ 8.4 ps, respectively. Around the half
revival the molecular axis distribution changes from aligned to antialigned in ∼ 1.5 ps
for CO2 and ∼ 700 fs for N2 .
For nonadiabatic alignment, the electric field of the alignment pulse torques themolecular axes towards its polarization axis. This torque creates a brief initial alignment in which the axes are aligned parallel to the electric laser field shortly after time
zero. Then the molecular axis distribution dephases and the sample becomes almost
isotropic. However periodic transient molecular alignment revivals (rephasing) occur
long after the end of the excitation pulse. This has the advantage that the laser pulse
is long gone before the molecular sample experiences revivals, which are therefore happening unperturbed from external fields. The delay times at which revivals occur are
determined by the rotational constant of the molecule. How these revival structures
occur is best explained quantum mechanically: The spectrum of the short alignment
pulse contains many frequency components. Therefore pairs of frequencies can drive
many Raman transitions (spaced by the selection rule ∆J = +/ − 2, 0). This cascaded
Raman process creates a coherent superposition of rotational levels a rotational wave
packet:Ψ(t) = |0 > exp(i0t/~) + |2 > exp(iE2 t/~) + |4 > exp(iE4 t/~) + ...

(4.12)

where |Ji is the rotational state and EJ = BJ(J + 1) the rotational energy and B =~2 /(2I) is the rotational constant of the molecule with I the moment of inertia. The
different components of the wavepacket evolve in time according to their energies, andperiodically come into phase again. After time Trot = h/2B, the full revival occurs
where all rotational levels are in phase. Less strong revivals occur at fractions of the140
full revival time.

4.4.2

Quantum mechanical description of rotational coherent wave packets

For a quantum mechanical treatment we refer to the work of Ortigoso and coworkers [114]. Briefly, we start with a molecule in the laser field where the interaction energy
is given by
Einteract = −d · E(4.13)

Here the dipole can be either a permanent electric dipole d, as e.g. in a heteronuclear molecule, or an induced dipole
d=α·E
where



(4.14)
0 
 α⊥ 0
α =  0 α⊥ 0 




0
0 α||

(4.15)

is the polarizability tensor with α|| and α⊥ the polarizabilities along the molecularaxis and perpendicular to the molecular axis.
For a linear or symmetric top molecule we can write an effective Hamiltonian
describing the interaction of the laser field with the dipole as well as a term for themolecular rotational energy:
1
Hef f (t) = B · J2 − E 2 (t)[(α|| − α⊥ )cos2 θ + α⊥ ]2(4.16)The time evolution of the wavefunction describing the molecular axis orientation
is described byi~ ∂ψ(t)
H(t)
=
ψ(t)
B ∂t
B

(4.17)

141
The Ansatz for the rotational wavepacket isψ(∆ω(t)) =X

dJ (∆ω(t))YJ,M(4.18)J

where∆ω(t) = (α|| − α⊥ ) ·E 2 (t)2B(4.19)and YJ,M are the spherical harmonics. One can solve for the time-dependent
coefficients dJ by inserting (4.18) into the time-dependent Schroedinger equation for
the rotational wavepacket (4.17).
Under the influence of the laser pulse an initial state |Ji , Mi i evolves into a timedependent molecular axis distribution A(θ, τ )(Ji ,Mi ) given by the probability of the rotational wavepacket |ψ(∆ω(t))|2 . However even in a supersonically cooled gas jet there
are several states |Ji , Mi i populated and therefore have to be thermally averaged to
calculate the expectation value of the molecular axis distribution:
1
Athermal (θ, τ ) =
Qrot

Ji X
=max

EJ

− kTi

ωJi exp

Ji =0

+Ji
X

hψ(∆ω(τ ))|ψ(∆ω(τ ))i(Ji ,Mi )(4.20)

Mi =−Ji

where the rotational partition function is given by
Qrot =

JX
i =∞

EJ
i

ωJi (2Ji + 1) exp− kT(4.21)

Ji =0and ωJi are factors giving the relative populations of the rotational levels due tonuclear spin statistics.
In the case of CO2 only even J values are occupied, whereas for N2 even and odd
J values are occupied.
A good parameter to describe the degree of alignment is the ensemble-average ofcos2 θ, called the alignment cosine (see Figure 4.10):

Z2< cos (θ)(τ ) >=Z
2

cos (θ)Athermal (θ, τ ) sin(θ)dθ/

Athermal (θ, τ ) sin(θ)dθ(4.22)

142
where sin(θ) is the geometrical weight factor in spherical coordinates and Athermal (θ) is
the axis probability distribution. It is shown in Figure 4.10 for CO2 versus delay after
the alignment pulse. The higher < cos2 θ >, the larger the number of molecules aligned
parallel to the polarization of the alignment laser. < cos2 θ >= 1 would correspond to a
fully aligned sample, < cos2 θ >= 0 would be fully antialigned (i.e. all axes perpendicular
to the alignment laser polarization) and an isotropic sample has a < cos2 θ >= 1/3. Notethat for the isotropic sample A(θ, τ ) = 0.5.

4.4.3

Practical considerations for strong molecular alignment

From the above considerations and from others [180] we find that the bigger thepolarizability anisotropy and the stronger the electric field of the alignment pulse, thestronger the alignment will be. Of course the maximum intensity that can be usedin the alignment pulse is limited by the onset of ionization, i.e. determined by themolecule’s ionization potential. In general, less polarizable molecules can withstandhigher intensities (as the nonresonant ionization rate scales with the polarizability),
compensating for their smaller polarizability. The only other quantity that influencesalignment is the temperature/rotational constant ratio T /B which gives the number of
initially populated rotational states. For a stronger alignment we want as few states as
possible to be initially populated. Therefore we can increase the degree of alignment
by decreasing the molecular rotational temperature. To achieve this, it can be useful toseed the molecules with another gas (buffer gas) [146] to further cool the sample in asupersonic expansion. This will not only increase the variation between minimum andmaximum of < cos2 θ >, but also increase the delay between alignment maximum andminimum in a revival. The background alignment between the revivals also increases
with decreasing temperature.
We also find that with increasing laser intensities the minima and maxima of< cos2 θ > increase, as shown in Figure 4.11. However we need to keep the laser intensity

0.50

0.45

0.45

0.40

0.40

2

0.35
0.30

2

0.35
0.30

11

Intensity / 10 W/cm
35
0.25
50
65

0.20
0

143
11

Intensity=65 10 W/cm
τ=140fs<cos (θ)>

2<cos (θ)>

0.50

2

2

T=16K
τ=140fs

4
6
time (ps)

0.25
8

10

Temperature
11K
15K
20K

0.20
0

2

4
6
time (ps)810

Figure 4.11: Calculated alignment cosine for N2 versus time after alignment pulse.
Left: dependence on alignment pulse intensity at fixed rotational temperature. Right:
dependence on temperature at fixed alignment pulse intensity.

low enough to not ionize the molecules by multiphoton ionization. This can be especiallycritical in a COLTRIMS apparatus where a large number of false coincidences can occur
due to these unwanted ionizations from the alignment beam. Of course, the method offield-free molecular alignment is restricted to molecules with anisotropic polarizability
i.e. there must be a large difference in polarizability along and perpendicular to themolecular axis. However, this is generally true for molecules for which alignment ismeaningful, i.e. not spherically symmetric molecules.
Another method to improve the degree of molecular alignment is the use of several
pulses for alignment. Using two-pulse alignment [90] an improvement of the alignment
cosine of ∼ 20% was achieved.

4.5

Measuring neutral-to-ionic transition dipoles: Angular Dependence of the Single-Photon Ionization of Aligned N2 and CO2
We demonstrate a new method which allows us to measure the orientation of thetransition dipole for nondissociative ionizations using single photon photoionization for
the first time. It also allows to measure dissociative ionizations which do not fulfill theaxial recoil approximation for the first time and may be used in future experiments to144
examine the validity of the axial recoil approximation in detail.

4.5.1

Motivation for this experiment

Why are we interested in measuring the angular orientation of molecular neutral to- ionic transition dipoles? In any system in which we want to control ionizationand make it happen efficiently, we need to assure that at least a portion of the transition dipole is parallel to the ionizing field. This transition dipole d is given by thematrix element of the dipole operator e · x between an initial, neutral molecular state|ψneutral i, and the final state hψionic |, consisting of the ion and the leaving photoelectronhψionic |ex|ψneutral i. When the transition dipole is parallel to the molecular axis, thenthe angular dependence of the ionization cross section is cos2 θ and the ionization yield is
maximized for an aligned sample, whereas for a perpendicular dipole it is sin2 θ and theyield is maximized for molecular axes perpendicular to the ionizing field (θ is the angle
between the polarization of the light source and the molecular axis). Knowledge of themolecular frame transition dipole hψionic |ex|ψneutral i between neutral and ionic statesof molecules is thus fundamental to understanding photoionization of molecules. The
calculation of transition dipole moments is substantially more difficult for bound-freetransitions than for bound-bound transitions. This is because in contrast to calculating transition dipole moments for neutral-to-neutral transitions (provided the electronic
structure for initial and final state is known), a correct treatment of the continuum wave
function of the free electron is required [97].
The difficulty in measuring molecular-frame transition dipoles arises because
gaseous molecules are isotropically oriented. In addition, relatively short femtosecond
duration NIR pulses for alignment and EUV probe pulses for probing the angular dependence of photoionization of molecules are needed. This is because the time duration
between alignment and antialignment of molecular axes during a fractional revival of
the rotational wave packet is on the order of 1000 s of femtoseconds. Of course these145
measurements also require a low pulse-to-pulse timing jitter of the EUV pulse withrespect to the IR alignment pulse so that the delay between pump and probe is welldefined. This is one reason why this experiment is difficult to implement at current
synchrotron or free electron laser facilities, as the EUV pulses there have large timing
jitters on the order of femtoseconds or even picoseconds.
By combining amplified femtosecond pulses to create field-free molecular alignment, with ionizing few-femtosecond EUV pulses, and momentum imaging of the resulting molecular fragment ions and photoelectrons using a COLTRIMS reaction microscope, we map the angular dependence of molecular photoionization yields for the
first time for a non-dissociative molecule. The observed modulation in ion yield as afunction of molecular alignment is attributed to the molecular frame transition dipole
moment of single-photon ionization to the X, A and B states of N2+ and CO2+ . Ourdata show that the transition dipoles for single-photon ionization of N2 and CO2 at 43
eV have larger perpendicular components than parallel ones. A direct comparison withpublished theoretical partial wave ionization cross-sections confirm these experimental
observations - which are the first results to allow such comparison with theory for boundcation states. These results also provide the first step towards a novel method for measuring molecular frame transition dipole matrix elements. As a side, we will also show
the orientational dependence of the transition dipole from IR strong-field ionization,
which is a multiphoton process.

4.5.2

Past measurements on transition dipoles

In past work, molecular frame neutral-to-ionic transition dipoles have been measured e.g. for molecules adsorbed on surfaces. In the case of CO, it is possible tomonitor the intensity of a particular shape resonance as a function of x-ray polarization
to determine if the molecule is lying flat or perpendicular to the surface [147]. Howevera surface can perturb the adsorbed molecules.

146
Transition dipoles have also been measured for dissociative ionization channels, bycoincidence measurement of ”fixed-in-space” photoelectron angular distributions following dissociative ionization [176]. In the simplest case of linear molecules, the fragment
ions recoil along the molecular axis and we can measure the momentum of the fragment ions. The angular distribution of photoelectrons with respect to the molecularaxis defined by the recoiling ions allows then to determine the molecular-frame transition dipole. This approach has been applied to both valence- [131] and inner-shell[131, 33, 175] ionization, but is limited to systems in which the ions dissociate rapidly,
i.e. faster than it would take the molecule to rotate between ionization and dissociation.
This condition is called the axial recoil approximation.
Note also that fragmentation processes into dissociating channels only make up a
few percent of the total ionization yield, so that a large fraction of ionizations cannot be
studied using this method. For example for CO2 the ratio of nondissociative ionizations
into CO2+ to the dissociative channel O+ + CO is ∼ 3 : 1. Therefore, measurements
of molecular frame transition dipoles for states undergoing non-dissociative ionization
have to date been very limited.
Experimental molecular frame transition dipole matrix elements for photoionization have also been determined previously by measurements of rotationally resolved
photoelectron angular distributions [128, 65, 66, 89, 115]. To date, this approach has
only been applied to hydride molecules and to the photoionization of selected highrotational levels of diatomic molecules, where the rotational spacings of the ion are
sufficiently large to resolve.
While all these approaches have produced beautiful and enlightening results,
both methods have their limitations. Thus, complementary approaches for determining
molecular frame transition dipole matrix elements are highly desirable.
It has long been proposed [131] that a perfectly aligned molecular sample (<cos2 θ >= 1) would enable the direct measurement of the molecular frame transition

147
dipoles for states undergoing non-dissociative ionization, which is the dominant process
in photoionization. In the case of gas phase molecules, adiabatic and non-adiabaticalignment methods have been extensively studied over the past decade [133, 47, 146].
Adiabatic alignment requires a very strong static electric field or a long laser pulse (picosecond to nanosecond), that slowly aligns the molecular axes along the laser polarization by exerting a torque on the induced dipole. Adiabatic alignment has recently beenused in an x-ray absorption experiment to study CF3 Br [121]. Non-adiabatic alignment
employs a short laser pulse to excite a coherent rotational wave packet, which undergoes
periodic rephasing (revivals) and transiently aligns the molecules. This approach has
the advantage of being field free and therefore more attractive for studying the interaction between non-perturbed free molecules and photons. Non-adiabatic alignment has
been used in a recent experiment, to probe alignment effects using EUV [92]. Suzuki
and coworkers [165] demonstrated the possibility of generating a rotational wave packet
by using a one-photon transition. The issue with this type of experiment lies in the
low degree of alignment they can produce in molecules. The theoretical limiting valueof < cos2 θ > is 0.6 for a pure parallel transition (Note that this value is only true
for the fraction of molecules that were excited. Most of the molecules however remainin the ground state.). However, the adiabatic and non-adiabatic alignment does nothave such limit. For example, a very high degree of alignment (< cos2 θ >= 0.92) has
been achieved in iodobenzene by Kumarappan et al.[88]. Experimental conditions suchas molecular rotational temperature and laser intensity can be optimized to increase
the degree of alignment. Of course, the method of field-free alignment is restricted tomolecules with anisotropic polarizability.
In this work we show that by combining non-adiabatic alignment using strong
femtosecond pulses with a reaction ”microscope”– molecular imaging apparatus, we
can use femtosecond EUV pulses to measure the relative single-photon ionization crosssection as a function of molecular alignment. As a result, we can directly obtain the148ratio between the parallel and perpendicular molecular frame transition dipoles. We
also compare the angular dependence of single-photon ionization with soft x-rays tothe angular dependence of multiphoton ionization by an intense femtosecond infrared(IR) laser field. We find that the N2+ and CO2+ multiphoton ionization ion yields are
maximized when the molecules are aligned with the polarization axis of an intense NIR
field. In contrast, for single-photon non-dissociative ionization by EUV pulses, the ionyields maximize when the molecules are aligned perpendicular to the polarization of the
x-rays. These measurements indicate that the ionizing transitions are predominantly
perpendicular for single-photon EUV ionization, and allow a direct comparison withtheory for the first time for these systems. Finally, we show that the single-photon
dissociative ionization channels N 2 → N + + N + e− and CO2 → O+ + CO + e− aremaximized when the molecules are aligned parallel to the EUV polarization, in contrast
to the non-dissociative ionization channels. These results provide the first step towards
direct measurement of molecular frame transition dipoles from highly aligned moleculesin the laboratory frame.
Lepine et al. [92] have performed similar experiments using a combination ofshort NIR pulses to align N2 and CO2 , and EUV light produced by high-harmonic
generation to probe the alignment. The principal difference between their work andour experiment is that their EUV beam was not energy-selected, but consisted of all
harmonic orders between ∼ 20 eV and 55 eV. In our experiment, we use multilayer
mirrors to select a single harmonic order - the 27th harmonic at ∼ 43 eV - with a few eV
bandwidth. This difference is important because the molecular frame transition dipoles,
and thus the relative amplitudes of the parallel and perpendicular transitions, are energy
dependent. Thus, the larger bandwidth of the previous measurements is expected tosmooth out any variations. In addition, although the potential of the approach for
threshold (non-dissociative) photoionization was discussed, the earlier measurements
focused on dissociative ionization processes, and no parent cation yield modulation was

149
observed. Their attempt to observe an alignment dependence of the angular-resolved
photoelectron spectrum of N2 was unsuccessful.
4.5.3

Experimental setup and technique for measuring angle dependent
photoionization of molecules

Our experiment begins with a gaseous sample of molecules which are isotropicallyoriented. To create field-free alignment in the molecular sample we employ a strong but
non-ionizing fs NIR laser pulse (∼ 4 · 1012 W/cm2 ) to impulsively excite a coherent
molecular rotational wavepacket. We then use few-femtosecond EUV pulses to measure
the yield of single-photon ionization as a function of time as the molecules undergofield-free alignment. This method to measure molecular neutral ionic transition dipoles
is widely applicable - the only requirement is that the molecules can be aligned. It isapplicable to nondissociative ionizations, as well as dissociative ionizations that do not
fulfill the axial recoil approximation.
BS 30 fs

140 fsIR alignment beam

delay
stage

glass block
IR probe beam

delay
stage

BS

BS
f=50cmf=50cme-

Argon filled
hollow waveguideAl filter

COLTRIMS
E,B
fieldsion

EUV probe beam
f=75cmtime&position
sensitive detectors

Mo/Si
multilayer
mirrors

supersonicmolecular beam
COLTRIMS

Figure 4.12: Experimental setup. An NIR (800 nm) alignment pulse of duration 140
fs first aligns the supersonically cooled N2 and CO2 molecules. Aligned molecules arethen ionized by either a delayed, 35 fs, NIR pulse or a ∼ 10 fs, 43 eV energy, EUV pulse(blue).

150
To measure the single-photon ionization yield during a rotational wave packet
revival in a small molecule, sub-picosecond EUV pulses are needed because of the shortduration of the revival. Therefore, in this experiment we use high harmonic generation
by a femtosecond laser to produce ultrafast (∼ 10 fs) EUV pulses as the source ofionizing radiation. The experimental setup is shown in Figure 4.12. We use a Ti:sapphire
amplifier system producing 2 mJ pulses, at a 2 kHz repetition rate, and with 35 fs pulse
duration, and split the output into pump and probe beams. The pump pulse, withintensity ∼ 4 · 1012 W/cm2 , is stretched to 140 fs to impulsively align the moleculesby creating a rotational wave packet, which periodically exhibits macroscopic fieldfree alignment around the polarization axes of the pump aligning pulse [114]. The
probe beam, with energy 1 mJ, is focused into an argon-filled hollow waveguide to
produce a comb of phase matched harmonics [135]. Using two Mo/Si multilayer mirrors
and an Aluminum filter (200 nm thick), we preferentially select soft x-ray harmonics
centered at ∼ 43 eV (27th harmonic), which are then focused non-collinearly with thepump beam into the molecular sample. The soft x-ray photon flux is estimated to be∼ 106 photons/pulse. The relatively large bandwidth of the EUV light precludes theresolution of vibrational (and even electronic) structure in the photoelectron spectra of
the N2+ and CO2+ , which have vibrational spacing of ∼ 0.1 − 0.4 eV. Alternatively, we
can use NIR light as the probe beam to ionize the molecule using multiphoton strongfield ionization that occurs at laser intensities around 3·1013 W/cm2 . Since multiphoton
ionization is a more sensitive probe of alignment, we first used the strong field ionization
signal to verify our alignment conditions.
To extract the angle dependent ion yield, a molecular supersonic gas jet is placedin a COLTRIMS (Cold Target Recoil Ion Momentum Spectroscopy) reaction microscope[51], which allows reconstruction of the full momentum vectors of all charged particles
resulting from ionization, with coincidence measurement capability. We exploit the
COLTRIMS coincidence and momentum imaging capabilities to distinguish different

151
ionization channels. We measure the kinetic energy Epe of photoelectrons detected incoincidence with the respective ions. This allows determination of the ion channel by
its vertical ionization energy Eion = hνEU V − Epe .
The ion yield was probed during the first half-revival for N2 (4.2 ps) and CO2 (21.0ps), where the molecular axis distribution changes from aligned to anti-aligned. The
variation of the angular distribution with delay during a rotational revival is effectively
the same as varying the angle between pump and probe polarization at a fixed timedelay corresponding to maximum molecular axis alignment. However, by using parallel
polarizations in the alignment and ionizing pulses, azimuthal symmetry is maintainedat all times, which simplifies the analysis.

4.5.4

Experimental Results: Angular Dependence of the Strong-Field
Ionization of Aligned N2 and CO2

In a first experiment we used strong field ionization to verify our method of extracting angle-dependent photoionization. As this is a multiphoton process, the angularcross section can be more strongly peaked than for single photon ionization. This canbe seen in the yield of N2+ , which peaks rather sharply around the aligned point, andtakes a rather broad dip around the antialigned point (see inset 4.14 (a)). From theobserved behavior of the ion yield we can immediately infer that the ionization crosssection is sharply peaked around 0 degrees and suppressed for all other angles. Froma fit of the ion yield versus delay we quantitatively extract the angle-dependent crosssection. An analogous analysis can be done for CO2 .
4.5.5

Experimental Results: Angular Dependence of the Single-Photon
Ionization of Aligned N2 and CO2

For single photon ionization the cross section is simply proportional to 1 + β · P2 ,where P2 is the second order Legendre polynomial and β is the parameter we extract

152
from our measurements. A β of 2 corresponds to a parallel dipole. This means thatmolecules are most efficiently ionized when the axis is parallel to the ionizing field. For
β of −1 we have a perpendicular dipole which means the ionization is most efficient foraxis perpendicular to the ionizing field.
Figure 4.13 shows the photoelectron spectra of N2 and CO2 , measured in coincidence with N2+ and N + , and CO2+ and O+ , respectively, following ionization by 43eV photons. Within our experimental resolution, these spectra agree with publishedphotoelectron spectra of CO2 and N2 , showing that single-photon ionization of N2 re+2
2 +sults primarily in the population of the X 2 Σ+
g , A Πu and B Σu states of N2 , andthat ionization of CO2 results primarily in the population of the X 2 Πg , A 2 Πu , B 2 Σ+u ,+and C 2 Σ+g states of CO2 . The ionization energy of N2 is 15.6 eV, and the dissociationenergy of N2+ is 8.7 eV, resulting in a dissociative ionization threshold of 24.3 eV [69].
Thus, with a 43 eV photon, photoelectrons with kinetic energy greater than ∼ 18.7 eV
are expected to be correlated with stable N2+ , while photoelectrons with kinetic energy
less than ∼ 18.7 eV are expected to be correlated with N + fragments. Given our experimental resolution, this assumption is consistent with Figure 4.13 (a). Similarly, theionization potential of CO2 is 13.8 eV and the dissociation energy of CO2+ is ∼ 5.3 eV,resulting in a dissociative ionization threshold of ∼ 19.1 eV. Photoelectrons with kinetic
energy greater than ∼ 23.9 eV should therefore be correlated with stable CO2+ . While
this is generally consistent with our observations, in contrast to N2 , some CO2+ appears
unstable for photoelectron energies up to ∼ 30 eV. This result may simply reflect the
bandwidth of the high-harmonic light. In addition, some CO2+ appears to be stable forphotoelectron energies down to about 18 eV. This observation may simply result fromthe larger number of internal degrees of freedom in CO2+ , resulting in a longer lifetime
before dissociation, and enabling competing non-dissociative decay mechanisms such as
fluorescence to stabilize the parent ion. This observation is also consistent with therelatively long dissociation timescale inferred below for the CO2+ C state.

153

40

photoelectron counts

(a)
+

N2

30

ionization
channel

20
+

10

N +N
dissociative
ionization
channel

0
0

10

20

energy [eV]

30

40

70

photoelectron counts

(b)
60
+

CO2

50

ionization
channel

40
30
20
10
0
0

+

O + COdissociative
ionization
channel10

20energy [eV]30

40

Figure 4.13: Photoelectron spectra in coincidence with (a) N2+ (red) and N + (blue) (b)CO2+ (red) and O+ (blue). With coincidence measurement, N2+ and CO2+ are found at
X, A and B state. N + is from N2+ inner valence states with binding energy > 24 eV.
O+ is from CO2+ C dissociative state (∼ 19 eV).

The yields for singly ionized N2 and CO2 as a function of time delay between
the alignment and EUV ionizing pulses, again in the region around the half revival,

154

2

cos (θ)(a) 0.45

N2

0.40
0.35
0.30
0.25

ionization channel
IR align,
IR probe

1.2

Normalized Yield

1.15

1.1

Normalized Yield

1.0

1.10

0.9
0.8
4.0
4.5
5.0
5.5
delay [picoseconds]

1.05

+

N +N

+

N2

1.00

0.95
3.0

3.5

4.0

4.5

5.0

5.5

delay [picoseconds]+(b) N + N dissociative ionization channel (EUV)+

N ionization channel (EUV) N ionization channel IR align, IR probe
1.6 2
90
120
12060
60
5
1.4
4
3 150
30
1.2
2
1
1.0
0 180
30 0
150
0.8
1
2
0.6
330
3 210
4
0.4
240
300
5
angle [degrees] 270
0.2
00.0 180
0.2
0.4
0.6
0.8
330
210
1.0
1.2
θ
1.4
EUV
240
300
1.6
angle θ [degrees] 270+

cross section [a.u.]cross section [a.u.]

2

Figure 4.14: (a) Upper panel: calculated alignment cosine (see text) for N2 versus timedelay. Main panel: EUV ionization yields from transiently aligned N2 . Solid (hollow)
symbols: N2+ (N + + N dissociation). Lines: numerical fitting. Inset: multiphoton(NIR) ionization yield of N2+ and its numerical fitting. (↓↑: aligned sample; ↔: antialigned sample). (b) Extracted angular dependence of the EUV photoionization crosssection to N2+ and N2+ dissociative states (N + ). Inset: extracted angular dependenceof multiphoton (IR) ionization of N2 . These angular dependencies were extracted, as
described in the text, from a fit to the delay-dependent yield data shown in (a).

155
are shown in Figure 4.14 and 4.15. The insets of these figures also show the ion yields
resulting from multiphoton ionization by an intense femtosecond NIR field. For the caseof multiphoton ionization, the N2+ and CO2+ yields are highest when the molecules arealigned with the polarization of the NIR field. However, for the case of single-photon
EUV ionization, the ion yield is at minimum when the EUV polarization is parallel tothe molecular axis. This surprising contrast clearly demonstrates the difference between
multi-photon and single-photon ionization. However, the origin of such difference is
not trivial, since the mechanism of multi-photon ionization is still an area of intense
investigation [120].

4.5.6

Discussion

Electronic transitions in linear molecules are generally classified as parallel or perpendicular according to whether the dipole is parallel or perpendicular to the molecularaxis, with the corresponding selection rule for the electronic angular momentum, Λ, of∆Λ = 0 and ∆Λ = ±1, respectively. Note that for the final state in photoionization,Λ
includes the electronic angular momentum of the ion and photoelectron. When themolecule is aligned parallel to the polarization axis of the light, parallel transitions areenhanced, and perpendicular transitions are diminished, while the opposite is true if themolecule is aligned perpendicular to the polarization axis of the light. Thus, the time(angular-) dependence of the ionization yield is a sensitive probe of the character of thetransition dipole, and the angle-dependent yield can be directly related to the molecular
frame dipole. Note, however, that limited resolution can complicate the process of extracting the direction of molecular frame dipoles, as several continua can contribute at agiven photon energy. For example, if the photoelectron energy resolution is insufficient+2 +to resolve different final electronic states, the N2 X 1 Σ+
g → N2 X Σg + ²pσu or ²f σu
+
0
0
2 +
and N2 X 1 Σ+
g → N2 B Σu + ² sσg or ² dσg photoionization processes, which all havethe same overall symmetry, will overlap.

156
CO2

0.35

2

cos (θ)(a) 0.40
0.30
0.25
1.15

ionization channel
IR align,
IR probe

Normalized Yield

1.05

Normalized Yield

1.00

1.10

0.95
20 21 22 23 24
delay [picoseconds]

+

1.05

O + CO

+

CO2

1.00

0.95
19

20

21

22

delay [picoseconds]

23

24

+

O + CO dissociative ionization channel (EUV)+
CO2 ionization channel (EUV)
1.6
CO ionization channel
120
60 IR90align, IR probe
1.4
120
60
1.6
1.2
1.2
30
150
0.8
1.0
0.4
150
30 0
0.0 180
0.8
0.4
0.6
0.8 210
330
0.4
1.2
240
300
1.6
0.2
angle [degrees] 270
0.0 180
0
0.2
0.4
0.6
0.8
330
210
1.0
1.2
θ
1.4
EUV
240
300
1.6
angle θ [degrees] 270(b)+cross section [a.u.]cross section [a.u.]

2

Figure 4.15: (a) Upper panel: calculated alignment cosine (see text) for CO2 versus
time delay. Main panel: EUV ionization yields from transiently aligned CO2 . Solid(hollow) symbols: CO2+ (O+ + CO dissociation). Lines: numerical fitting. Inset:
multiphoton (IR) ionization yield of CO2+ and its numerical fitting. (↓↑: aligned sample;↔: antialigned sample). (b) Extracted angular dependence of the EUV photoionization
cross section to CO2+ and CO2+ dissociative states (O+ ). Inset: extracted angulardependence of multiphoton (IR) ionization of CO2 .

157
To quantitatively determine the angular dependence of EUV photoionization,
we first calculate the time dependence of the angular probability distribution A(θ, τ )of molecular axes for the rotational revival following the method developed by Ortigoso et al.[114]. We use the experimental parameters for alignment pulse durationand laser intensity of 140 fs, 3.5 · 1012 W/cm2 for CO2 , and 140 fs, 5 · 1012 W/cm2
for N2 . The degree of alignment of the sample is given by the alignment cosine, i.e.
the average of cos2 (θ) over the calculated molecular axis distribution:< cos2 (θ) >=R
R
cos2 (θ)A(θ, τ ) sin(θ)dθ/ A(θ, τ ) sin(θ)dθ. The calculated alignment cosine for theconditions of the EUV single-photon ionization experiment is given for N2 and CO2 in
Fig. 4.14 (a) and 4.15 (a), upper panel, respectively. Then the ionization yield versus
R
delay τ is given by an angle integral: Y ield(τ ) = A(θ, τ )σ(θ) sin(θ)dθ, where θ isthe angle between the direction of polarization of the light and the molecular axes. We
expand the angular dependence of the ionization cross-section in terms of Legendre polynomials σ(θ) = C ·(1+βP2 (cos(θ))+γP4 (cos(θ))+...). For single-photon ionization, theionization cross-section only contains the second order term: σ(θ) = C ·(1+βP2 (cos(θ)).
Note, the β value in the equation is different from the one extracted from photoelectron
angular distributions. It simply represents the anisotropy of angular dependence of theionization cross-section. To remove the effect of possible EUV intensity fluctuations,the yield in the presence of the alignment beam is normalized by the yield without thealignment pulse present. We obtained β = −0.43 ± 0.13 by fitting to the N2+ ion yielddata shown in Figure 4.14. A theoretical value ( βtheory = −0.46) for this parameter canbe derived from the results of recent calculations on the photoionization of N2 at thisenergy [16]. To do this, we used the equation: β = (2 − σperp /σpara )/(1 + σperp /σpara ).
σperp and σpara are the total cross-sections of perpendicular transitions and parallel
ones taken from the reference. The theoretical calculations [16] indicate that at 43 eV,photoionization to the A state makes up more than half of the total ionization crosssection and is strongly perpendicular in character, while photoionization to the X and B

158
states has mixed parallel and perpendicular character, resulting in overall perpendicularcharacter for the unresolved continua.
In Figure 4.14 we also show the N + yield from the dissociative channel leading to
N + + N . This process can be separated into transitions leading to two final states - the−1 2 Σ+ state - with the F 2 Σ+ state dominant. These channels can be
F 2 Σ+
g and (2σg )gg

separated in our experiment, and thus we can characterize the orientation of their transition dipoles separately: N + ions were measured in coincidence with photoelectrons,
and energy filters were applied. For the F 2 Σ+g state, the ion energy filter was between
0.08−1.84 eV, and the electron energy filter was between 8−20 eV. For the (2σg )−1 2 Σ+gstate, the ion energy filter was between 1.84 − 5.32 eV, while the electron energy filter−1 2 Σ+was between 3.5 − 13.5 eV. We find the β values for the F 2 Σ+g state and (2σg )gstates are 0.47 ± 0.20, and 0.18 ± 0.20, respectively. These correspond to ratios between
the perpendicular and parallel dipole contributions of ∼ 1 and 1.54 respectively using
σperp /σpara = (2 − β)/(1 + β). These two dissociative channels leading to N + + N are
the only ones relevant to this study that have been accessible in previous studies using
momentum imaging techniques. In experiments with 40.8 eV photons, Hikosaka andEland [64] have measured a transition ratio σperp /σpara of 0.23 for the F 2 Σ+g state, and−1
a ratio σperp /σpara of 0.6 for the (2σg )−1 2 Σ+g state. Although the ratio for the (2σg )2 Σ+ state is higher than that for the F 2 Σ+ state in both experiments, the absoluteggvalues are quite different. This discrepancy may result in part from the different photon
energies in the two experiments.
In Figure 4.15, we show the O+ yield from the dissociative channel leading toO+ + CO, as well as the non-dissociative CO2+ yield. It is obvious that the dissociative
process results from a predominantly parallel transition, while the non-dissociative process results from a predominantly perpendicular one. As in the case of N2 , our resultsfor CO2 are in agreement with theoretical results (βtheory = −0.43) [15]. Specifically, at
43 eV, perpendicular transitions are expected to dominate photoionization to the X, A,

159
and B states of CO2+ , while parallel transitions are expected to dominate photoionization to the C state, of CO2+ , which mainly predissociates into O+ + CO. We find a β
value of −0.67 ± 0.19 for the data shown in Figure 4.15. These data are for CO2+ ionsdetected in coincidence with electrons in the energy range from 20 to 30 eV which wasdone to remove the signal from the NIR alone. Because of its low ionization potentialof 13.78 eV, CO2 can even be ionized by the alignment NIR pulse. However, sincethese ions are generated in coincidence with low energy electrons, they therefore can befiltered from the data. We also studied the electron yield for comparison. For electrons
with energy between 20 eV and 30 eV, which are formed in coincidence with both CO2+
and O+ + CO, we find a value of −0.36 ± 0.10. This observation is consistent with thefact that the parallel component for the transition to the C state of CO2+ is stronger
than the perpendicular component. This results in a larger value than is observed bymonitoring CO2+ ions, for which the C state does not contribute.
We also obtain the angular dependence of the photoionization cross-section forthe dissociative channel O+ + CO. We find a β value of +0.51 ± 0.15 (see Figure 4.15).
The O+ + CO channel likely proceeds by dissociation from the C 4σg channel of CO2+
[92, 15, 96]. The angular ionization cross section of this dissociative channel could thus
not be measured before.
Although the O+ ion signal shows a strong dependence on the alignment of themolecular axis, the O+ angular distribution at a given delay (or given alignment of
the molecular axis to the polarization axis) is essentially isotropic at all delays. Thisobservation is consistent with the results of Lepine et al. [92]. In particular, the long
lifetime of the intermediate state in this dissociation channel therefore appears to violate axial recoil approximation, leading to an isotropic momentum distribution andmaking it impossible to determine the transition dipole with conventional methods.
However, Dowek et al. [35] reported an anisotropic parameter of ∼ 1 for O+ angular
distribution from CO2 dissociative ionization at 35 eV. Even though this discrepancy

160
between their and our results might be due to the photon energy difference, it needs
further investigation to clarify. Theoretically [15, 99] it has been predicted that a broad
shape resonance structure contributes to the ionization to the C state between 30 and
45 eV. The corresponding continuum orbital is of σu symmetry, making this a paralleltransition. The experimental β parameter is in agreement with the theoretical value
at 43 eV of βtheory = 0.84, which was obtained as described above for N2 . The otherpartial wave contribution σg − > πu is a perpendicular transition and is not affected by
the shape resonance. Thus, our method provides a direct way to probe this otherwise
elusive shape resonance [14] in free CO2 molecules.
We summarize extracted experimental anisotropy parameters for different ionization channels and their theoretical values in the following table.
Table 4.2: Comparison of Anisotropy Parameters (β) between Experiment and Theory
molecules
N2
CO2

4.5.7

ionization channels
N2+ (X,A,B)+
N2+ (F 2 Σ+
g , N + N)+
−1
2+
N (2σg )Σg , N + + N )CO2+ (X,A,B)
CO2+ (C 4σg , O+ + CO)

βexperiment−0.43 ± 0.13
+0.47 ± 0.20
+0.18 ± 0.20
−0.67 ± 0.19
+0.51 ± 0.15

βtheory-0.46-/-/-0.43+0.84

Conclusion and Outlook

In conclusion, we have developed a novel method for measuring the direction ofmolecular transition dipoles. This new method does not require fragmentation of themolecule to determine the direction of the transition dipole, and allows measurementof non-dissociative bound-free transitions in N2+ and CO2+ for the first time. Moreover,
our approach also allows determination of the direction of the transition dipoles for dissociative ionization, where for example, the excited lifetime of the state is comparable
to or longer than the molecular rotation period i.e. where the axial recoil approxi-

161mation breaks down, as we show for the O+ + CO channel. The method presented
here should be also applicable to larger and more complicated molecules, and can beextended to measurements of excited molecular states. With increased electron energy
resolution, future experiments should also allow selective measurements for individual
final states. Finally, as pointed out in the Introduction, a particularly interesting extension of this method will be to measure photoelectron angular distributions of highlyaligned molecules. Such measurements will ultimately allow the determination of bothquantitative molecular-frame transition dipole matrix elements and their phase-shiftdifferences, i.e. a ”complete” ionization experiment [83].

4.6

Towards molecular-frame photoelectron angular distributions
This section describes progress towards the measurement of molecular-frame pho-toelectron angular distributions, including electrons from nondissociative ionization
channels. For a strongly aligned sample, the lab frame is identical to the molecular
frame, and molecular frame photoelectron angular distributions can be measured. These
measurements become more difficult for lower degree of alignment, where molecularframe information gets blurred in the lab-frame. Here we describe some initial resultsin obtaining molecular-frame photoelectron angular distributions.
This work is related to the work by Tsubouchi and Suzuki. They created a rotational wave packet of NO molecules in an excited electronic state using a femtosecond
laser pulse. From a detailed analysis of the time-dependent lab-frame photoelectron
angular distribution, photoionization transition dipole moments were determined [165].
We measure the angular dependence of photoelectrons from the nondissociative
ionization channel N2+ and CO2+ from aligned and antialigned molecules. To date,attempts to see such effects have been unsuccessful [92]. Fig. 4.16 shows a typical lab
frame electron momentum distribution. Figure 4.17 (a) shows the difference in lab-frame
photoelectron counts for an aligned versus isotropic molecular sample for CO2 (black

1.5
0
-3

-1.5

Electron Py (atomic units)

3

162

-3

-1.5

0
1.5
electron Pz (atomic units)

3

Figure 4.16: 2D projection of lab frame momentum distribution of photoelectrons fromN2 .

symbols) and N2 (red symbols), and Fig. 4.17(b) shows difference in photoelectron
counts for an antialigned versus isotropic sample for CO2 and N2 . The plotted angle
here is between photoelectron emission and EUV polarization, which is parallel to the
NIR alignment beam polarization. For the aligned case there is an overall negative
difference because the nondissociative ionization channel is suppressed for the aligned
sample, as discussed above for the ion yield. Around 90◦ however the difference tends
toward zero again in agreement with above results on the ion yield. For the antialigned
case in Fig. 4.17(b) we expect to see a positive yield and an increase of photoelectronsat 0◦ . Indeed we observe evidence of this in the case of CO2 (Note that the data containgeometrical sin(θ) factor. The reason why it does not completely go to zero at zero

163
degrees is that the data were more averaged along the x-axis), perhaps due to its higher

50

Yield difference (aligned - unaligned)

Yield difference (aligned - unaligned)

anisotropic polarizability, but not for N2 .
150

molecules aligned
CO2
N2

0

100

-50

-100

(a)

-150
0

20

40

60

80

angle w.r.t EUV polarization [degrees]molecules anti-aligned
CO2
N2

50

0

(b)
-50
0

20

40

60

80

angle w.r.t EUV polarization [degrees]

Figure 4.17: Difference in photoelectron angular distributions for aligned (a) and antialigned (b) molecules [155].

In future experiments we would like to extract the molecular frame photoelectron angular distribution from observables measurable with the COLTRIMS reaction
microscope and the photoelectron angular distribution in the lab frame. To this end,
COLTRIMS acquisition and analysis codes and a Matlab program were implemented
for future experiments.
Figure 4.18 shows the relevant coordinates. We are particularly interested inphotoelectron angular distributions from molecular nondissociative ionizations using
the experimental techniques described above. We can measure the photoelectron distribution in the lab frame, Counts(θez ) where θez is the angle between the measured
electron momentum and the lab z-axis (equal to the polarization axis of the alignment
pulse and ionization pulse). The photoelectron distribution in the laboratory frame isgiven byZ
Counts(θez ) = sin(θez )Zdϕedθi sin(θi ) · A(θi , τ ) · σ(θi ) · B(θez , ϕe , θi )(4.23)

Here, sin(θez ) is a geometrical weighting factor, A(θi , τ ) is the angular probability

164

pz
E

θi

molecular
axis

θez

θei
ePpar

N

eP1

φe

px
ePperppy

Figure 4.18: Coordinates used for the description of molecular-frame photoelectron
angular distributions: The EUV electric field points in the lab-frame z-axis. The blackarrow defines the molecular axis - here at an angle θi w.r.t. the lab frame z-axis. eP1 is
the momentum of an electron detected at an angle θez w.r.t. the lab frame z-axis. The
electron emission angles in the molecular frame are θei and φe (defined w.r.t the normal
N on the plane spanned by E and the molecular axis).

distribution of molecular axes, which is calculated [114], and θi is the angle of themolecular axis in the lab frame. The angular dependence of the ionization cross section
σ(θi ) is expressed in terms of Legendre polynomials,

σ(θi ) = C · (1 + β · P2 (cos(θi )))(4.24)and β gives the orientation of the transition dipole, which can be obtained in a
separate measurement (as was described in section 4.5 above). B(θez , ϕe , θi ) is the photoelectron angular distribution (PAD) in the molecular frame. We express B(θez , ϕe , θi )through Legendre polynomials,

165

0

0

B(θez , ϕe , θi ) = A · (1 + β · P2 (cos(θei )) + γ · P4 (cos(θei )))0(4.25)

0

Here β , γ are fit parameters (more than two fit parameters can be easily included
if necessary), and θei is the angle between the momentum of the photoelectron and themolecular axis. As we want to express B(θez , ϕe , θi ) as a function of lab frame angle θez ,we express the angle θei in the molecular frame by angles in the lab frame (see Figure4.18):

cos(θei ) = ~i · ~e = sin(θi ) · sin(θez ) · cos(ϕe ) + cos(θi ) · cos(θez )(4.26)The ion axis is chosen in the lab xz-plane (which is possible, as the ion distribution
is azimuthally symmetric) ~i = (sin(θi ), 0, cos(θi )), and the electron momentum directionis ~e = (sin(θez ) cos(ϕe ), sin(θez ) sin(ϕe ), cos(θez ). The expression for Counts(θez ) canR
be understood as follows: the integral dθi sin(θi )·A(θi , τ )·σ(θi )·B(θez , ϕe , θi ) averages
the PAD over all possible molecular axis orientations, weighted with the probability offinding a molecule with a given angle, A(θi , τ ), and weighted with the probability ofRionizing such a molecule, σ(θi ). The integral dϕe finally sums over all azimuthal electron angles, as we do not expect any azimuthal dependence of the electron distribution,
because the alignment (and therefore the molecular axes distribution) and ionizationgeometries are azimuthally symmetric. The information about the PAD is given by the00

fit parameters β , γ . Of course, the ansatz 4.25 is oversimplified, and can only provide
a very limited amount of information on the actual molecular-frame PAD. However it isstraightforward to replace the right-hand side with a more general expression in termsof spherical harmonics [128].

166

4.7

Other results obtained with COLTRIMSThis section shows unfinished results of several other molecules peeked at with

the COLTRIMS reaction microscope.

4.7.1

Coulomb explosion following photoionization of N2 O at 43 eV

40000

N2O+

30000

20000

10000

O+

NO+

N+

N2+

0
0

2000

4000
6000
8000
TOF1 (nanoseconds)

10000

Figure 4.19: Time of flight spectrum of all charged fragments of N2 O irradiated with
43 eV light. N2 O+ : nondissociative ionization. All other fragments may arise from
dissociative ionization O+ + N2 and N + + N O, or from Coulomb explosion O+ + N2+
or N + + N O+ .

Figures 4.19 - 4.21 show results obtained on the EUV photoionization of N2 O at 43
eV. Importantly, Figure 4.21 shows a projection of the ion angular distribution of N O+
from the Coulomb explosion of doubly ionized N2 O2+ → N O+ + N + . Surprisingly,
this ion angular distribution is almost isotropic. From earlier results we had expecteda very anisotropic distribution β ∼ 1.5 [2]. However the data in [2] show a missing
data point exactly at 43 eV. In addition, Eland and coworkers [150] showed evidence

6000

TOF2 (ns)
7200
8400

9600

167

4400

5200

6000
4400
TOF1 (ns)

5200

6000

Figure 4.20: Coincidence filters applied. Left: unfiltered T OF2 vs T OF1 image of two
ion fragments detected in coincidence from the fragmentation of N2 O. Right: The
Coulomb-explosion channels of interest, N2 O → N O+ + N + and N2 O → N2+ + O+ areselected out by a filter relating T OF2 and T OF1 via the momentum conservation in the
Coulomb explosion.

of a ”probable” metastable state of the N2 O2+ dication, assigned as 2 3 Π at 42.5 eV,a ”somewhat surprising” finding given multiple potential curve crossings in this energy
region. A metastable state with a lifetime longer than a rotational period would beconsistent with an isotropic angular distribution of fragments.

4.7.2

EUV photoionization of O2 at 43 eV

Figure 4.22 shows the O+ fragment from the photoionization of O2 . This fragmentshows multiple dissociation channels: The assignment of ion channels in the figure
caption follows Vrakking and coworkers [75].

-100 -80 -60 -40 -20 0 20 40 60 80 100

Py (atomic units)168-100 -80 -60 -40 -20 0 20 40 60 80 100
Pz (atomic units)
Figure 4.21: 2D projection of the momentum image of N O+ from the Coulomb explosion
N2 O → N O+ + N + .

-100 -80 -60 -40 -20 0 20 40 60 80 100

Py (atomic units)

169

12

34

-100 -80 -60 -40 -20 0 20 40 60 80 100
Pz (atomic units)
Figure 4.22: The momentum image of O+ following dissociative ionization of O2 shows
4 dissociation channels, 1: O+ (2 P) + O(3 P), 2: O+ (4 S) + O(3 P), 3: O+ (4 S) + O∗ (1 D),
4: O+ (4 S) + O(3 P).

Chapter 5
Outlook

The results described in this thesis can be a starting point for many future experiments. The combination of ultrafast EUV and NIR radiation with the coincidence
capabilities of the COLTRIMS detection technique is a powerful tool for the studyof time-resolved correlations of electrons and ions. While the experiments using the
COLTRIMS apparatus done so far in our group have employed EUV pulses which
are several femtoseconds in duration, future experiments could well benefit from the attosecond duration EUV pulses presented in Chapter 3, enabling attosecond spectroscopy
experiments.
It has become clear that future EUV experiments in molecular physics would
greatly benefit from state resolution. In general, the use of lower EUV photon energies
and EUV mirrors with narrower reflectance bandwidth will allow better energy resolution. The easily energy-tunable EUV radiation produced in this thesis, together with asetup for easy exchange between mirrors for selecting different harmonics will thus be
useful for experiments in molecular and materials experiments. Part of this has alreadybeen implemented by designing a setup consisting of 2 EUV mirrors in a z-configuration.
The two rotatable EUV mirrors consist of pie slices, each coated for different center energies. Such a setup will essentially create a ”table-top synchrotron”, and will e.g. allow
one to measure the orientation of the transition dipole (and transition dipole matrix
elements) with state resolution, as opposed to the averaged results presented in this171
thesis. In addition it will simplify the analysis of photoelectron angular distributions.
Overall, I am convinced that the field of attosecond science is just at its beginning,
and that there are exciting times to come for ultrafast EUV radiation. Isolated attosecond pulses generated from long driving pulses using waveguide geometries will be usefulfor the study of fast electron dynamics. Easily energy-tunable single-femtosecond, near
Fourier transform limited pulses will be an excellent source for the study of the coupledmotion of nuclei and electrons, as it occurs e.g. near conical intersections in molecules.
Sophisticated pump-probe experiments in combination with NIR pulses or electron wave
packets, together with more and more sensitive detection techniques, and the utilizationof coherent EUV imaging techniques, will open up more and more applications for thisunique table-top light source.

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