Imaging Nuclear Motion During the Photofragmentation of Halomethane Molecules Triggered by Ultraviolet Light

Imaging Nuclear Motion During the Photofragmentation of Halomethane Molecules Triggered by Ultraviolet Light
Author: Farzaneh Ziaee
Publisher:
Total Pages: 0
Release: 2022
Genre:
ISBN:

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Understanding the photoexcitation of molecules and visualizing the ensuing dynamics on their natural time scale is essential for our ability to describe and exploit many fundamental processes in different areas of science and technology. Prominent examples of such processes include, among many others, the adverse impacts of different classes of molecules on the ozone layer in atmospheric chemistry, light conversion into electricity through photovoltaics, photocatalysis, and some essential biological processes like vision and photosynthesis. Studies of molecular dynamics triggered by photon-molecule interaction underpin our understanding of many of these phenomena by adding the intermediate state to the "before-and-after" view of such photochemical or photobiological reactions. While identifying the initial molecular structure at equilibrium and determining the final products are crucial steps for the reaction characterization, understanding the dynamics connecting these initial and final states is essential for comprehending how the reaction really happens and potentially controlling its outcome. In other words, besides the "static" view of photo-induced reactions, identifying all intermediate states involved and mapping their spatio-temporal evolution are of great interest and importance. Since photoexcitation often induces coupled electron and nuclear motion on Angström spatial and femtosecond time scales, resolving such dynamics in space and time represents a significant scientific and technological challenge. Experimental tools to address this challenge have recently become available with the development of femtosecond lasers and imaging techniques capable of visualizing the evolving molecular structure. The present thesis aims to investigate the photodissociation dynamics of halomethane molecules triggered by ultraviolet (UV) light using coincidence ion momentum imaging as a primary structural characterization tool. Halomethanes are often considered as prototypical systems for molecular photodissociation in the UV domain. Due to the complicated excited-state structure driving the photochemistry of these molecules, they exhibit rich dynamics while being small enough to still allow for a detailed theoretical treatment. The primary goal of this work is to disentangle the photo-induced reaction channels, including direct and indirect dissociation pathways, and to visualize the motion of the individual molecular fragments in each of these channels. The photofragmentation reactions considered here include two- and three-body dissociation, transient isomerization and molecular halogen formation. The experiments are carried out at two different excitation wavelengths, 263 nm and 198 nm, which enables varying the dominant reaction pathways. To carry out these measurements, the 3rd and 4th harmonics of a 790 nm Ti: Sa femtosecond laser are used to initiate the dynamics of interest, which are then probed by multiple ionization and Coulomb explosion induced by an intense 790 nm pulse arriving after a variable time delay. The ions created in such pump-probe experiments are detected employing COLd Target Recoil Ion Momentum Spectroscopy (COLTRIMS). To facilitate interpreting the experimental results, they are compared to an extensive set of Coulomb explosion simulations. More specifically, this thesis describes three major studies. The first one is a set of time-resolved measurements on iodomethane (CH3I) photodissociation in the A-band, one of the best-studied reactions in ultrafast photochemistry. Here, the focus is on a detailed characterization of direct dissociation dynamics by Coulomb explosion imaging (CEI) and disentangling the competing reaction pathways involving single- and multi-photon excitations. The coincident measurement mode and an improved time resolution of 40-45 fs allowed us to observe a new feature in the two-body CEI pattern of this well-studied reaction, which was predicted theoretically but not yet observed experimentally, and to identify signatures of two- and three-photon processes populating Rydberg and ionic states. The second part of this work focuses on time-resolved studies of bromoiodomethane (CH2BrI) and chloroiodomethane (CH2ICl) photofragmentation in the A-band at 263 nm and, in particular, on imaging the co-fragment rotation. Here, the main objectives are to evaluate the effects of halogen-atom substitution on molecular dynamics and map the time evolution of individual photodissociation pathways. For these molecules, photoabsorption in the A-band predominantly breaks the C-I bond, with weaker but non-negligible contribution from the C-Br (or C-Cl) bond cleavage. Coincident two-body CEI analysis is used to map both of these channels, as well as a minor contribution from molecular halogen (IBr or ICl) formation. Three-body CEI patterns offer a deeper insight into the dynamics of these reactions and, in addition, reveal clear signatures of the three-body dissociation, which - at this wavelength - is most likely driven by the two-photon absorption. The three-body analysis also suggests that some fragmentation pathways pass through a transient linearized configuration, which is reached within ~100 fs from the initial photoabsorption and decays on a comparably fast time scale. One of the interesting aspects of dihalomethanes photodissociation in the A-band is that, unlike CH3I, where the excess energy is primarily channeled into translational motion, a significant portion of the available energy is partitioned into rotational excitation. Carbon-halogen bond cleavage results in the rotation of the molecular co-fragment, which can be unambiguously traced in the coincident three-body CEI maps for the corresponding dissociation channel. In this work, such rotational motion is directly imaged for the dissociation of either halogen atom, resulting in a "molecular movie" of the dissociating and rotating molecule. The third group of experiments described in this thesis includes time-resolved studies of bromoiodomethane and diiodomethane (CH2I2) photofragmentation in the B-band at 198 nm. In this part, the main goal is to trace the wavelength dependence of the photochemical reaction pathways. For CH2BrI, we observe a reversal of the branching ratio of C-I and C-Br bond cleavage compared to the 263 nm data, in agreement with earlier spectroscopic and theoretical studies. However, at 198 nm, three-body dissociation and molecular halogen formation become dominant photofragmentation channels for both molecules. Finally, the CH3I photodissociation is also studied in the B-band at 198 nm, where the excitation of the lowest-lying Rydberg states is expected to trigger pre-dissociation dynamics. Although no in-depth data analysis and modeling for this reaction have been carried out, the two-body CEI results clearly demonstrate the pre-dissociation nature of CH3I fragmentation at this wavelength, reflected in a broad, diffuse dissociation band, which is very different from distinct dissociation features observed for direct dissociation processes. Moreover, the data exhibit a pronounced oscillatory structure with a periodicity of 130-140 fs, which is visible only within the pre-dissociation lifetime of the excited state (~1.5 ps). While the exact origin of this structure remains unclear and will be a subject of further analysis and theoretical work, it most likely reflects the bound-state vibrational motion, which lasts until it pre-dissociates. The work presented in this thesis represents a significant step towards a better understanding of the UV-driven photochemistry of halomethanes and contains several examples of direct visualization of the atomic motion during these photochemical reactions. Our experimental approach enabled us to identify and disentangle different dissociation pathways and track their time evolution. The experimental methodology described here can be directly applied to investigate the light-driven nuclear motion in other molecular systems with different light sources.

Imaging Photo-induced Dynamics in Halomethane Molecules with Coincident Ion Momentum Spectroscopy

Imaging Photo-induced Dynamics in Halomethane Molecules with Coincident Ion Momentum Spectroscopy
Author: Balram Kaderiya
Publisher:
Total Pages: 0
Release: 2021
Genre:
ISBN:

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Molecular transformations triggered by the absorption of light are of tremendous importance in our day-to-day life, science, and technology. Examples of such "photo-induced" reactions include, among many others, photosynthesis, solar energy conversion, and mechanisms behind human vision. Besides knowing the final outcome of such reactions, for many scientific and technological applications it is crucially important to understand how they evolve in time, and how the motion of individual atoms leads to a certain outcome. For decades, resolving these processes in time represented a severe experimental challenge since the atomic motion involved is extremely fast. The availability of ultrashort, femtosecond laser pulses in combination with novel molecular imaging techniques provides experimental tools needed to address this challenge. This thesis describes the application of coincident ion momentum imaging setup, sometimes called "a reaction microscope", for studies of photo-induced dynamics in halomethane molecules (CH2I2, CH2ICl, CH3I). The main objective of this work is to visualize light-induced breaking, rearrangement and formation of molecular bonds, and to determine relevant mechanisms and time scales. Halomethanes are often considered as model systems for studying such prototypical photochemical events because they are small enough to allow for reasonable electronic structure calculations and for coincidence detection of all molecular fragments, while being large enough to be of chemical relevance and to undergo some fundamental chemical transformations. The work described here covers three different regimes of light-molecule interaction: (1) ionization and fragmentation by an intense near-infrared (NIR) field, (2) excitation of a neutral molecule by a single ultraviolet (UV) photon; and (3) ionization and fragmentation by a single extreme ultraviolet (XUV) photon. We specifically focus on several aspects of halomethane photochemistry that are of general importance, have been actively discussed in literature, and yet are difficult to access using more established imaging or spectroscopic techniques. More specifically, we first characterize molecular response to a single intense femtosecond NIR pulse at 800 nm, identifying and disentangling different ionization and fragmentation channels, and their signatures in various coincident observables. Then we apply multiple ionization and rapid dissociation ("Coulomb explosion") by such a pulse as a tool to map molecular dynamics in pump-probe experiments. In this approach, the information on molecular geometry at the time when the probe pulse arrives is extracted from the coincident measurement of the 3D momentum vectors of the detected fragment ions. We start with the NIR pump / NIR probe experiments on CH2I2 and CH2ICl molecules, aimed at characterizing bound and dissociating wave packets induced by a strong NIR field. Here, we find that both, dissociation dynamics and molecular halogen elimination (I2 or ICl) are mainly governed by the large-scale bending vibrations of the molecule, even though (weak) signatures of stretching vibrations can be also observed in the spectra. Focusing on the I2 (or ICl) elimination channel, which requires breaking two carbon-halogen bonds and formation of a new bond between the two halogen atoms, we demonstrate how it can be disentangled from the other fragmentation channels, and find that it is dominated by a direct, "synchronous" pathway. Then we apply the same approach and the same NIR probe pulses to study the photoexcitation of diiodomethane (CH2I2) by a femtosecond UV pulse at 266 nm in a UV pump / NIR probe experiment. Here, in addition to two-body dissociation and I2 elimination channels, we also observe a significant contribution of three-body dissociation. This channel can be easily separated in our triple-coincidence measurements, but is notoriously difficult to identify with most of the other techniques. Besides that, we find signatures of transient CH2I-I isomer formation within the first 100 femtoseconds after the initial photoexcitation. While the picosecond-scale isomerization of CH2I2 was clearly demonstrated earlier in the liquid-phase experiments in solution, and was shown to occur due to the interaction with the solvent, the existence of a much faster, intra-molecular isomerization pathway for isolated molecules in a gas phase was debated in literature. In this work, we provide direct evidence of such ultrafast, sub-100 fs CH2I2 isomerization, and demonstrate that the decay of this short-lived isomer opens up an additional pathway for molecular iodine elimination. Finally, we have performed a complementary study on CH2ICl and CH3I molecules employing short extreme ultraviolet pulses (XUV) from FLASH II free-electron laser facility in Hamburg, Germany. Here, one femtosecond XUV pulse at ~ 53 nm central wavelength is used to initiate the dynamics, mainly by single-photon ionization, while the second identical pulse is used to probe the evolution of the created ionic-state wave packets. Employing the same ion momentum imaging setup, we map different dissociative ionization channels and observe signature of intramolecular electron transfer between different sites of a dissociating molecular ion. In contrast to the results of earlier FEL experiments on X-ray inner-shell photoionization of dissociating halomethanes, which could be readily explained using the classical over-the-barrier charge transfer model, our data for valence XUV ionization suggest a more subtle dependence of the charge transfer probability on the internuclear distance, likely determined by the delocalization of molecular orbitals. Overall, the work presented in this thesis advances our understanding of different pathways in strong-field and single-photon induced photochemistry of halomethanes, and demonstrates an efficient and visual approach for mapping transient reaction intermediates. The tools and methodology presented here can be applied to study a broad range of ultrafast photochemical reactions, and can be useful for many strong-field imaging and control applications.

The Chemical Bond

The Chemical Bond
Author: Ahmed Zewail
Publisher: Elsevier
Total Pages: 333
Release: 1992-05-14
Genre: Science
ISBN: 008092669X

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This inspired book by some of the most influential scientists of our time--including six Nobel laureates--chronicles our emerging understanding of the chemical bond through the last nine decades and into the future. From Pauling's early structural work using x-ray and electron diffraction to Zewail's femtosecond lasers that probe molecular dynamics in real time; from Crick's molecular biology to Rich's molecular recognition, this book explores a rich tradition of scientific heritage and accomplishment. The perspectives given by Pauling, Perutz, Rich, Crick, Porter, Polanyi, Herschbach, Zewail, and Bernstein celebrate major scientific achievements in chemistry and biology with the chemical bond playing a fundamental role. In a unique presentation that also provides some lively insights into the very nature of scientific thought and discovery, The Chemical Bond: Structure and Dynamics will be of general interest to scientists, science historians, and the scientifically inclined populous.

Organic Peroxy Radicals

Organic Peroxy Radicals
Author: P. D. Lightfoot
Publisher:
Total Pages: 5
Release: 1992
Genre:
ISBN:

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Cold Chemistry

Cold Chemistry
Author: Olivier Dulieu
Publisher: Royal Society of Chemistry
Total Pages: 692
Release: 2017-12-06
Genre: Science
ISBN: 1788013557

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Recent years have seen tremendous progress in research on cold and controlled molecular collisions, both in theory and in experiment. The advent of techniques to prepare cold and ultracold molecules and ions, to store them in optical lattices or in charged quasicristalline structures, and to use them in crossed or merged beam experiments have opened many new possibilities to study the most fundamental aspects of molecular interactions. At the same time, theoretical work has made progress in tackling these problems and accurately describing quantum effects in complex systems, and in proposing viable options to control chemical reactions at ultralow energies. Through tutorials on both the theoretical and experimental aspects of research in cold and ultracold molecular collisions, this book provides advanced undergraduate students, graduate students and researchers with the foundations needed to understand this exciting field.

Femtochemistry

Femtochemistry
Author: Ahmed H. Zewail
Publisher: World Scientific
Total Pages: 622
Release: 1994
Genre: Science
ISBN: 9789810217365

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These two volumes on Femtochemistry present a timely contribution to a field central to the understanding of the dynamics of the chemical bond. This century has witnessed great strides in time and space resolutions, down to the atomic scale, providing chemists, biologists and physicists with unprecedented opportunities for seeing microscopic structures and dynamics. Femtochemistry is concerned with the time resolution of the most elementary motions of atoms during chemical change -- bond breaking and bond making -- on the femtosecond (10-15 second) time scale. This atomic scale of time resolution has now reached the ultimate for the chemical bond and as Lord George Porter puts it, chemists are near the end of the race against time. These two volumes cover the general concepts, techniques and applications of femtochemistry.Professor Ahmed Zewail, who has made the pioneering contributions in this field, has from over 250 publications selected the articles for this anthology. These volumes begin with a commentary and a historical chronology of the milestones. He then presents a broad perspective of the current state of knowledge in femtochemistry by researchers around the world and discusses possible new directions. In the words of a colleague, "it is a must on the reading-list for all of my students ... all readers will find this to be an informative and valuable overview."The introductory articles in Volume I provide reviews for both the non-experts as well as for experts in the field. This is followed by papers on the basic concepts. For applications, elementary reactions are studied first and then complex reactions. Volume I is complete with studies of solvation dynamics, non-reactive systems, ultrafast electron diffraction and the control of chemical reactions.Volume II continues with reaction rates, the concept of elementary intramolecular vibrational-energy redistribution (IVR) and the phenomena of rotational coherence which has become a powerful tool for the determination of molecular structure via time resolution. The second volume ends with an extensive list of references, according to topics, based on work by Professor Zewail and his group at Caltech.These collected works by Professor Zewail will certainly be indispensable to both experts and beginners in the field. The author is known for his clarity and for his creative and systematic contributions. These volumes will be of interest and should prove useful to chemists, biologists and physicists. As noted by Professor J Manz (Berlin) and Professor A W Castleman, Jr. (Penn State): femtochemistry is yielding exciting new discoveries from analysis to control of chemical reactions, with applications in many domains of chemistry and related fields, e.g., physical, organic and inorganic chemistry, surface science, molecular biology, ... etc.

Electronic and Photoelectron Spectroscopy

Electronic and Photoelectron Spectroscopy
Author: Andrew M. Ellis
Publisher: Cambridge University Press
Total Pages: 302
Release: 2005-01-13
Genre: Science
ISBN: 113944185X

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Electronic and photoelectron spectroscopy can provide extraordinarily detailed information on the properties of molecules and are in widespread use in the physical and chemical sciences. Applications extend beyond spectroscopy into important areas such as chemical dynamics, kinetics and atmospheric chemistry. This book aims to provide the reader with a firm grounding of the basic principles and experimental techniques employed. The extensive use of case studies effectively illustrates how spectra are assigned and how information can be extracted, communicating the matter in a compelling and instructive manner. Topics covered include laser-induced fluorescence, resonance-enhanced multiphoton ionization, cavity ringdown and ZEKE spectroscopy. The volume is for advanced undergraduate and graduate students taking courses in spectroscopy and will also be useful to anyone encountering electronic and/or photoelectron spectroscopy during their research.

71st International Symposium on Molecular Spectroscopy

71st International Symposium on Molecular Spectroscopy
Author: Benjamin J. Mccall
Publisher: Createspace Independent Publishing Platform
Total Pages: 302
Release: 2016-05-25
Genre:
ISBN: 9781533053909

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The International Symposium on Molecular Spectroscopy is the premier annual meeting in this exciting and interdisciplinary field. The symposium uniquely combines plenary talks from world leaders in the field with parallel sessions comprising shorter talks, many presented by graduate students, and fosters a collegial and collaborative atmosphere with a multitude of formal and informal interactions. Registration and housing costs are kept low to enable entire research groups to attend, and in fact most senior people in the field gave their very first conference presentation at this symposium (to a very friendly audience). A wide range of topics is covered, from theory to experiment, from gas-phase to condensed-phase, from low resolution to ultra-high resolution, from the microwave to the ultraviolet, and from fundamental science to applications such as astronomy and atmospheric science. Each year's meeting also includes three "mini-symposia" on topics of special interest.

High Tc Superconductor Thin Films

High Tc Superconductor Thin Films
Author: L. Correra
Publisher: Elsevier
Total Pages: 908
Release: 2012-12-02
Genre: Technology & Engineering
ISBN: 0444600256

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Interdisciplinary research on superconducting oxides is the main focus of the contributions in this volume. Several aspects of the thin film field from fundamental properties to applications are examined. Interesting results for the Bi system are also reviewed. The 132 papers, including 8 invited, report mainly on the 1-2-3 system, indicating that the Y-Ba-Cu-O and related compounds are still the most intensively studied materials in this field. The volume attests to the significant progress that has been made in this field, as well as reporting on the challenging problems that still remain to be solved.

Chiral Analysis

Chiral Analysis
Author: Kenneth W. Busch
Publisher: Elsevier
Total Pages: 721
Release: 2011-10-13
Genre: Science
ISBN: 0080469280

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Chiral Analysis covers an important area of analytical chemistry of relevance to a wide variety of scientific professionals. The target audience is scientific professionals with an undergraduate background in chemistry or a related discipline, specifically organic chemists, researchers in drug discovery, pharmaceutical researchers involved with process analysis or combinatorial libraries, and graduate students in chemistry. Chapters have been written with the nonspecialist in mind so as to be self-contained. * Broad coverage - spectroscopic and separation methods covered in a single volume * Up-to-date and detailed review of the various techniques available and/or under development in this field * Contributions from leading experts in the field