Molecular dynamics and photoionisation processes: from strong-fields to soft X-rays

This thesis comprises of a set of time and energy-resolved photoelectron spectroscopy studies of polyatomic molecules exposed to radiation ranging from the IR to soft X-ray region of the spectrum. Chapter 1 provides an introduction to molecular photochemistry, wavepacket dynamics and ionisation mechanism ranging from weak single photon ionisation to strong-field ionisation in intense laser fields. In Chapter 2 an experiment to probe excited state wavepacket dynamics in the molecule NO2 is presented. This experiment is based on using the channel-resolved above-threshold ionisation technique as a multi-dimensional probe of nonadiabatic dynamics in polayatomics molecules. The complex roles of one-photon excitation, multiphoton excitation to higher-lying neutral states, multi-channel neutral and ionic dissociation are examined and complications of using strong-fields to probe photochemistry are outlined. Chapter 3 deals with a VUV/UV time-resolved photoelectron velocity map imaging (VMI) study of Rydberg-valence mixing in high-lying excited states of acetone (CH3-CO-CH3). Details are provided of the implementation of a high-flux femtosecond VUV source based on non-collinear four-wave mixing. The VMI results show evidence of non-adiabatic evolution from the initially prepared 3dyz electronic state to the lower-lying 3p/3s states and subsequent relaxation of these Rydberg states to the pipi* electronic state on a few hundred femtosecond timescale. Chapters 4 and 5 deal with energy-resolved synchrotron radiation studies of the core-level ionisation, excitation and Auger decay in CH3I. Detailed assignments and analysis of the angular distributions connected with the I 4s, 4p and 3d orbitals are provided. These studies are a necessary precursor to aid in the interpretation of time-resolved data obtained using recently developed laboratory and facility based soft X-ray sources. Finally, Chapter 6 provides a summary of the different opportunities offered by performing time-resolved photoelectron spectroscopy in various wavelength regimes and provides an outlook for future work utilising novel ultrafast light sources

Dissecting Sub-Cycle Interference in Photoelectron Holography

Multipath holographic interference in strong-field quantum tunnel ionization is key to revealing sub-Angstrom attosecond dynamics for molecular movies. This critical sub-cycle motion is often obscured by longer time-scale effects such as ring-shaped patterns that appear in above-threshold ionization (ATI). In the present work, we overcome this problem by combining two novel techniques in theory and experimental analysis: unit-cell averaging and time-filtering data and simulations. Together these suppress ATI rings and enable an unprecedented highly-detailed quantitative match between strong-field ionization experiments in argon and the Coulomb-quantum orbit strong-field approximation (CQSFA) theory. Velocity map images reveal fine modulations on the holographic spider-like interference fringes that form near the polarization axis. CQSFA theory traces this to the interference of three types of electron pathways. The level of agreement between experiment and theory allows sensitive determination of quantum phase differences and symmetries, providing an important tool for quantitative dynamical imaging in quantum systems.Comment: 13 Pages, 8 figure

High Repetition-Rate Pulse Shaping of a Spectrally Broadened Yb Femtosecond Laser

We demonstrate compression and shaping of few cycle pulses from a high average power Ytterbium laser system. The pulses from a commercial 20 W, 100 kHz Yb laser system are spectrally broadened in two-stages using gas-filled, stretched hollow-core fibers and then compressed and shaped in an acousto-optic modulator-based pulse-shaper. The pulse-shaper allows for compression, characterization, and shaping all in one system, producing ~10 fs pulses with 50 uJ of energ

Time-resolved multi-mass ion imaging: femtosecond UV-VUV pump-probe spectroscopy with the PImMS camera

The Pixel-Imaging Mass Spectrometry (PImMS) camera allows for 3D charged particle imaging measurements, in which the particle time-of-flight is recorded along with $(x,y)$ position. Coupling the PImMS camera to an ultrafast pump-probe velocity-map imaging spectroscopy apparatus therefore provides a route to time-resolved multi-mass ion imaging, with both high count rates and large dynamic range, thus allowing for rapid measurements of complex photofragmentation dynamics. Furthermore, the use of vacuum ultraviolet wavelengths for the probe pulse allows for an enhanced observation window for the study of excited state molecular dynamics in small polyatomic molecules having relatively high ionization potentials. Herein, preliminary time-resolved multi-mass imaging results from C$_2$F$_3$I photolysis are presented. The experiments utilized femtosecond UV and VUV (160.8~nm and 267~nm) pump and probe laser pulses in order to demonstrate and explore this new time-resolved experimental ion imaging configuration. The data indicates the depth and power of this measurement modality, with a range of photofragments readily observed, and many indications of complex underlying wavepacket dynamics on the excited state(s) prepared

Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide

Auger electron spectra following excitation or ionization of the I 3d level in CH3I have been recorded with horizontally or vertically plane polarized synchrotron radiation. These spectra have enabled the Auger electron angular distributions, as characterized by the β parameter, to be determined. The I 3d photoionization partial cross section of CH3I has been calculated with the continuum multiple scattering approach, and the results show that in the photon energy range over which Auger spectra were measured, the I 3d cross section exhibits an atomic-like behavior and is dominated by transitions into the εf continuum channel. In this limit, the theoretical value of the alignment parameter (A20) characterizing the core ionized state in an atom becomes constant, independent of photon energy. This theoretical value has been used to obtain the Auger electron intrinsic anisotropy parameters (α2) from the β parameters extracted from our normal (non-resonant) molecular Auger spectra. The resulting anisotropy parameters for the M45N45N45 transitions in CH3I have been compared to those calculated for the corresponding transitions in xenon, and the experimental and theoretical results are in good agreement. Anisotropy parameters have also been measured for the M45N1N45, M45N23N45, and M45N45O23 transitions. For the M45N1N45 and M45N23N45 Auger decays in CH3I, the experimentally derived angular distributions do not exhibit the strong dependence on the final ionic state that is predicted for these transitions in xenon. Resonantly excited Auger spectra have been recorded at 620.4 and 632.0 eV, coinciding with the I 3d5/2 → σ* and 3d3/2 → σ* transitions, respectively. The resulting Auger electron angular distributions for the M4N45N45 and M5N45N45 decays were found to exhibit a higher anisotropy than those for the normal process. This is due to the larger photo-induced alignment in the neutral core excited state. For a particular Auger transition, the Auger electron kinetic energy measured in the resonantly excited spectrum is higher than that in the normal spectrum. This shift, due to the screening provided by the electron excited into the σ* orbital, has been rationalized by calculating orbital ionization energies of I 3d excited and I 3d ionized states in CH3I

Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

Pump-probe measurements aim to capture the motion of electrons and nuclei on their natural timescales (femtoseconds to attoseconds) as chemical and physical transformations take place, effectively making molecular movies with short light pulses. However, the quantum dynamics of interest are filtered by the coordinate-dependent matrix elements of the chosen experimental observable. Thus, it is only through a combination of experimental measurements and theoretical calculations that one can gain insight into the internal dynamics. Here, we report on a combination of structural (relativistic ultrafast electron diffraction, or UED) and spectroscopic (time-resolved photoelectron spectroscopy, or TRPES) measurements to follow the coupled electronic and nuclear dynamics involved in the internal conversion and photodissociation of the polyatomic molecule, diiodomethane (CH2I2). While UED directly probes the 3D nuclear dynamics, TRPES only serves as an indirect probe of nuclear dynamics via Franck-Condon factors, but it is sensitive to electronic energies and configurations, via Koopmans\u27 correlations and photoelectron angular distributions. These two measurements are interpreted with trajectory surface hopping calculations, which are capable of simulating the observables for both measurements from the same dynamics calculations. The measurements highlight the nonlocal dynamics captured by different groups of trajectories in the calculations. For the first time, both UED and TRPES are combined with theory capable of calculating the observables in both cases, yielding a direct view of the structural and nonadiabatic dynamics involved

Time-resolved site-selective imaging of predissociation and charge transfer dynamics: The CH3I B-band

The predissociation dynamics of the 6s (B2E) Rydberg state of gas-phase CH3I were investigated by time-resolved Coulomb-explosion imaging using extreme ultraviolet (XUV) free-electron laser pulses. Inner-shell ionization at the iodine 4d edge was utilized to provide a site-specific probe of the ensuing dynamics. The combination of a velocity-map imaging (VMI) spectrometer coupled with the pixel imaging mass spectrometry (PImMS) camera permitted three-dimensional ionic fragment momenta to be recorded simultaneously for a wide range of iodine charge states. In accord with previous studies, initial excitation at 201.2 nm results in internal conversion and subsequent dissociation on the lower-lying A-state surface on a picosecond time scale. Examination of the time-dependent yield of low kinetic energy iodine fragments yields mechanistic insights into the predissociation and subsequent charge transfer following multiple ionization of the iodine products. The effect of charge transfer was observed through differing delay-dependencies of the various iodine charge states, from which critical internuclear distances for charge transfer could be inferred and compared to a classical over-the-barrier model. Time-dependent photofragment angular anisotropy parameters were extracted from the central slice of the Newton sphere, without Abel inversion, and highlight the effect of rotation of the parent molecule before dissociation, as observed in previous © 2020 The Author(s). Published by IOP Publishing Ltd Printed in the U

Disentangling sequential and concerted fragmentations of molecular polycations with covariant native frame analysis

Using covariance analysis methods, we study the fragmentation dynamics of multiply ionized 1- and 2-iodopropane. Signatures of isomer-specific nuclear motion occurring during sequential fragmentation pathways are identified.</jats:p