Time-Resolved Photoionisation Studies of Polyatomic Molecules

Time-Resolved Photoionisation Studies of Polyatomic Molecules
Author: Martin Alex Bjørnholst
Publisher: Springer Nature
Total Pages: 155
Release: 2020-08-03
Genre: Science
ISBN: 3030536297

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This book explores how structure impacts the dynamics of organic molecules in an extensive and impressive range of femtosecond time-resolved experiments that are combined with state-of-the-art theoretical approaches. It explores an area of molecular dynamics that remains largely uncharted and provides an extraordinary overview, along with novel insights into the concept of the dynamophore – the functional group of ultrafast science. Divided into four parts, this book outlines both experimental and computational studies on the VUV photoinduced dynamics of four cyclic ketones and one linear ketone, the ring-opening and dissociative dynamics of cyclopropane, and the potential ultrafast intersystem crossing in three methylated benzene derivatives. Model systems for the disulfide bond and the peptide bond, both of which are related to the structure of proteins, are also investigated. This highly informative and carefully presented book offers a wealth of scientific insights for all scholars with an interest in molecular dynamics.

Photoionization and Photodetachment

Photoionization and Photodetachment
Author: Cheuk-Yiu Ng
Publisher: World Scientific
Total Pages: 1415
Release: 2000
Genre: Science
ISBN: 9812813470

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Owing to the advances of vacuum ultraviolet and ultrafast lasers and third generation synchrotron sources, the research on photoionization, photoelectrons, and photodetachment has gained much vitality in recent years. These new light sources, together with ingenious experimental techniques, such as the coincidence imaging, molecular beam, pulsed field ionization photoelectron, mass-analyzed threshold ion, and pulsed field ion pair schemes, have allowed spectroscopic, dynamic, and energetic studies of gaseous species to a new level of detail and accuracy. Profitable applications of these methods to liquids are emerging.This invaluable two-volume review consists of twenty-two chapters, focusing on recent developments in photoionization and photodetachment studies of atoms; molecules, transient species, clusters, and liquids.

Photoionization Dynamics of Polyatomic Molecules

Photoionization Dynamics of Polyatomic Molecules
Author: Paul Hockett
Publisher:
Total Pages:
Release: 2009
Genre:
ISBN:

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The work presented in this thesis was carried out with the ultimate aim of learning about the photoionization dynamics of polyatomic molecules. This is a complex problem; in order to obtain sufficient experimental data to shed light on the dynamics careful measurement of photoelectron angular distributions (PADs) is required. Ideally these measurements are rotationally-resolved, and the angular distributions measured correspond to the formation of the molecular ion in a single rotational state. The ionization event, in the dipole approximation, can be completely described by the dipole matrix elements. If sufficient experimental data to determine the radial components of the matrix elements and associated phases, the dynamical parameters, can be obtained the photoionization experiment may be said to be complete. Analysis of such experiments requires that the initial state of the molecular system is also known, to this end resonance-enhanced multi-photon ionization (REMPI) schemes can be used in order to populate a single quantum state prior to ionization. The experiments presented here follow this methodology, with various REMPI schemes used to prepare (pump) and ionize (probe) the molecule under study, and the velocity-map imaging (VMI) technique used to (simultaneously) record the photoelectron spectra and angular distributions. Two molecules have been studied experimentally, acetylene (C2H2) and ammonia (NH3). In both cases dynamical parameters pertaining to the formation of specific states (vibronic or vibrational) of the molecular ion have been determined from experimental data. Additionally, in the ammonia work, rotationally-resolved photoelectron images were obtained.

Coulomb Explosion Imaging of Polyatomic Molecules After Photoionization with X-rays and Strong Laser Fields

Coulomb Explosion Imaging of Polyatomic Molecules After Photoionization with X-rays and Strong Laser Fields
Author: Utuq Ablikim
Publisher:
Total Pages:
Release: 2017
Genre:
ISBN:

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Imaging the structures of molecules, understanding the molecular dynamics in onization and dissociation processes and, most importantly, observing chemical reactions, i.e. the making and breaking of chemical bonds in real time, have become some of the most exciting topics in the atomic and molecular physics. The rapid advances of experimental tools such as synchrotron radiation light sources, free-electron lasers and continuing advances of tabletop femtosecond ultrashort lasers that provide laser pulses at a variety of wavelengths have opened new avenues for understanding the structure of matter and the dynamics of the chemical interactions. In addition, significant improvements in computational techniques and molecular dynamic simulations have provided complementary theoretical predictions on structures and chemical dynamics. The Coulomb explosion imaging method, which has been developed and applied in many studies in the last three decades, is a powerful way to study molecular structures. The method has mostly been applied to small diatomic molecules and to simple polyatomic molecules. In this thesis, Coulomb explosion imaging is applied to study the structure of isomers, molecules that have the same chemical formula but different chemical structures. Specifically, by taking inner-shell photoionization as well as strong-field ionization approaches to ionize and fragment the molecules and by using coincidence electron-ion-ion momentum imaging techniques to obtain the three-dimensional momentum of fragment ions, structures of isomers are distinguished by using the correlations among product ion momentum vectors. At first, the study aims to understand if the Coulomb explosion imaging of geometrical isomers can identify and separate cis and trans structures. Secondly, in order to extend the application of the Coulomb explosion imaging method to larger organic molecules to test the feasibility of the method for identifying structural isomers, photoionization studiesof 2,6- and 3,5-difluoroiodobenzene have been conducted. In addition, using the full three-dimensional kinematic information of multi-fold coincidence channels, breakup dynamics of both cis/trans geometric isomers and structural isomers, and in particular, sequential fragmentation dynamics of the difluoroiodobenzene isomers are studied. Furthermore, for each study, Coulomb explosion model simulations are conducted to complement the experimental results. The results of the Coulomb explosion imaging reseach in this thesis paves the way for future time-resolved Coulomb explosion imaging experiments aiming to understand the transient molecular dynamics such as photoinduced ring opening reactions and cis/trans isomerization processes in gas-phase molecules.

Ion-electron Coincidence Studies of Femtosecond Dynamics Triggered by Extreme Ultraviolet Photoionization of Atoms and Molecules

Ion-electron Coincidence Studies of Femtosecond Dynamics Triggered by Extreme Ultraviolet Photoionization of Atoms and Molecules
Author: Seyyed Javad Robatjazi
Publisher:
Total Pages: 0
Release: 2021
Genre:
ISBN:

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Photoelectron spectroscopy employing X-ray and extreme ultraviolet (XUV) radiation is one of the most important experimental methods to study the electronic structure of atoms, molecules, and solids. Recent developments of XUV and X-ray sources with ultrashort pulse durations, like free-electron lasers (FELs) and high-order harmonics of infrared lasers, enabled combining this approach with a concept of a time-resolved measurement, where a pair of synchronized short light pulses is used to initiate and observe a physical or chemical process of interest. Among other advances, such combination turned out to be particularly useful for atomic physics and gas-phase femtochemistry, where femtosecond or even sub-femtosecond short-wavelength radiation can be used to trigger the dynamics in high-lying states previously inaccessible for time-resolved measurements and offers a variety of novel schemes to probe light-induced electronic and nuclear motion. One of the key challenges for time-domain studies employing short-pulsed radiation sources is that they are necessarily broadband and, thus, typically populate a broad range of atomic of molecular states. The main goal of this thesis is to develop an experimental approach that enables state-selective analysis of the dynamics induced by such broadband femtosecond pulses in the XUV domain, and to apply it to study several exemplary reactions in photoionized molecules. Since reducing the bandwidth of the XUV pulse would ultimately limit the achievable temporal resolution, in this work the challenge of state selectivity is addressed by employing photoelectron-photoion and photoion-photoion coincident measurements. In the experimental apparatus developed as a part of this thesis, a double-sided velocity map imaging (VMI) spectrometer for coincident detection of electrons and ions is combined with a femtosecond pump-probe setup that includes a near-infrared (NIR) laser and a fiber-based XUV source based on high-order harmonics generation. This instrument has been commissioned, characterized, and applied to several time-resolved experiments on atomic and molecular targets. More specifically, this thesis describes three different sets of experiments. First, a brief overview of several XUV-NIR pump-probe measurements addressing two-color single, double or triple ionization of atoms is presented. Here, the main focus is set on capturing generic characteristic features of the corresponding two-color signals, and on revealing physical mechanisms determining their "transient" or "steady" behavior with respect to the time delay between the XUV and NIR pulses. The second series of experiments focuses on exploring coupled electronic and nuclear dynamics in XUV-ionized CO2 molecule probed by the synchronized NIR pulse. This study, which constitutes the central part of the thesis, relies on the detection of the photoelectron that reveals which electronic state is initially populated, in coincidence with ionic fragments, which provide information on the specific dissociation channel of the molecular ion after the interaction with both pulses. Here, we observe signatures of an electron-hole wave packet motion near a conical intersection of two low-lying cationic states, trace rotational dynamics determined by the dependence of the state-specific XUV photoionization cross section on molecular orientation, and disentangle the contributions of individual states to different dissociation pathways. The third series of experiments aims at studying nuclear dynamics in XUV-ionized alcohol molecules, focusing on the channels involving ultrafast hydrogen motion. Here, ion mass spectrometry measurements on methanol and its deuterated isotopologue CH3OH and CD3OH show that, depending on a specific XUV wavelength, the formation of molecular hydrogen or trihydrogen cations can be either dominated by the channels combining the hydrogen from the oxygen site with one or two hydrogens from the methyl carbon, or by the ejections of all hydrogen atoms from the methyl group. Coincident electron spectra for specific ionic fragments enable linking these channels to the calculated dissociation pathways leading to H2+ or H3+ formation. Finally, we present the results of XUV-NIR pump-probe experiments on ethanol, where a transient enhancement of particular dissociation channels has been observed. The experimental methodology presented in this work can be readily extended to a broad range of molecular systems, including both, molecular ions and high-lying excited states of the neutral molecules. At the same time, highly-differential data on small polyatomic molecules like CO2, methanol, and ethanol presented here, can be used to benchmark theoretical models for XUV ionization of these prototypical systems, improving our general understanding of light-induced molecular dynamics.

Vector Correlations in Dissociative Photoionization of Small Polyatomic Molecules

Vector Correlations in Dissociative Photoionization of Small Polyatomic Molecules
Author: Mogens Lebech
Publisher:
Total Pages: 317
Release: 2003
Genre:
ISBN:

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Dissociative photoionization of small polyatomic molecules, here N20 and CO2, induced by VUV linearly polarized synchrotron radiation is studied using the vector correlation method, in conditions where photoionization leads to one ion, one neutral fragment, and one electron. The vector correlation method consists in measuring the velocity vectors of the photoion and photoelectron produced in each event. The velocity spectrometer combines time-of-flight resolved and position sensitive ion-electron coincidence detection. Ions and electrons are extracted from the interaction zone by a uniform electric field, which ensures a complete collection of both particles. Electrostatic lenses are implemented in the spectrometer in order to increase the velocity vector resolution. The ion-electron kinetic energy correlation derived from the magnitude of the velocity vectors for the coincident events allows one to identify the reaction pathway for each process, in terms of the intermediate N2O+ or CO2+ valence or inner-valence ionic state, or resonant N20** autoionizing state, and the dissociation limit characterized by the electronic states of both fragments and the vibrational distribution of the molecular fragment. The spatial analysis, correlating the two velocities and the polarization axis of the light, determines, for each process, the polar and azimuthal dependence of the molecular frame photoelectron angular distribution, for any orientation of the molecular axis with respect to the polarization axis. The results are presented in terms of four Fij functions which contain the most complete information about the photoionization dynamics for each process: their partial wave analysis gives access to the transition moments. A large number of reactions are identified, and anisotropies in the photoelectron angular distribution in the molecular frame are observed. Selected results obtained for N2O are compared with multichannel Schwinger configuration interaction calculations.

Advances In Multi-photon Processes And Spectroscopy, Vol 2

Advances In Multi-photon Processes And Spectroscopy, Vol 2
Author: Shih-i Chu
Publisher: World Scientific
Total Pages: 410
Release: 1986-05-01
Genre:
ISBN: 9814507954

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This volume focuses on the recent rapid growth in both experimental and theoretical studies of multiphoton processes and multiphoton spectroscopy of atoms, ions and molecules in chemistry, physics, biology, material sciences, etc. It contains papers readable by active researchers and by those who intend to enter it. Theory and experiment are equally emphasized, and each review article is written in a self-contained manner by experts in the field so that readers learn the subject without much preparation.