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Diffractive Imaging Of Laser Induced Molecular Reactions With Kiloelectron-Volt Ultrafast Electron Diffraction, Yanwei Xiong

Department of Physics and Astronomy: Dissertations, Theses, and Student Research

Capturing the structural changes during a molecular reaction with ultrafast electron diffraction (UED) requires a high spatiotemporal resolution and sufficiently high signal-to-noise to record the signals with high fidelity. In this dissertation, I have focused on the development of a tabletop gas phase keV-UED setup with a femtosecond temporal resolution. A DC electron gun was employed to generate electron pulses with a high repetition rate of 5 kHz. The space charge effect in the electron pulse was ameliorated by compressing the 90 keV electron pulse longitudinally with a time varying electric field in an RF cavity. The velocity mismatch between …

Roaming Transition States And Highly Accurate Thermochemistry: A Pepico Study Of Two Small Combustion Systems, Kyle John Covert

University of the Pacific Theses and Dissertations

Two small combustion systems, methyl hydroperoxide (CH₃OOH) and 2-propanol ((CH₃)₂CHOH), were studied using imaging photoelectron photoion coincidence spectroscopy (iPEPICO), which combines photoelectron spectroscopy and photoionization mass spectrometry to detect coincident photoelectron-photoion pairs. In the photon energy range of 11.4–14.0 eV, energy selected CH₃OOH⁺ ions dissociate into CH₂OOH⁺, HCO⁺, CH₃⁺, and H₃O⁺ ions. The lowest-energy dissociation channel is the formation of the cation of the smallest “QOOH” radical, CH₂OOH⁺. A statistical rate model fitted to the …

Photofragment Imaging Fast Ion Beams, Michael D. Johnston Jr.

Doctoral Dissertations

Metal-containing ions have been the subject of much research due to their roles in catalytic activation and small cluster chemistries. However, they can be difficult to study both experimentally and theoretically, and new approaches are needed. The goal of the research described here is to characterize the electronic structures and thermodynamics of metal-containing ions using gas-phase spectroscopy experiments performed on a powerful new instrument. Presented in the following chapters are the details of a recently built velocity map imaging mass spectrometer that is capable of imaging the photofragments of trap-cooled (≥7K) ions produced in a versatile ion source. This instrument …

The Investigation And Characterization Of The Reaction Of 2-Methylfuran And 2-Methyl-3-Buten-2-Ol With O(3p) And The Photodissociation Of Xylyl Bromide Isomers, Yasmin Fathi

Master's Theses

This thesis has studied the oxidation behavior of different biofuels or additives, 2-methyl-3-buten-2-ol and 2-methylfuran, in combustion experiments at the Chemical Dynamics Beamline held at the Advanced Light Source of the Lawrence Berkley National Laboratory. The oxidation of these fuels were initiated through O(³P) and the combustion experiments were analyzed using a multiplexed chemical kinetics photoionization mass spectrometer with tunable synchrotron radiation. Products of the different reactions were identified using kinetic profiles and further characterized using the photoionization spectra. The amount of each species was calculated using branching fractions.

Additionally, the unimolecular dissociation of the xylyl bromide isomers …

A New Set Of Potential Energy Surfaces For Hco: Influence Of Renner-Teller Coupling On The Bound And Resonance Vibrational States, Steve Alexandre Ndengué, Richard Dawes, Hua Guo

Chemistry Faculty Research & Creative Works

It is commonly understood that the Renner-Teller effect can strongly influence the spectroscopy of molecules through coupling of electronic states. Here we investigate the vibrational bound states and low-lying resonances of the formyl radical treating the Renner-Teller coupled X2A' and Ã2A" states using the MultiConfiguration Time Dependent Hartree (MCTDH) method. The calculations were performed using the improved relaxation method for the bound states and a recently published extension to compute resonances. A new set of accurate global potential energy surfaces were computed at the explicitly correlated multireference configuration interaction (MRCI-F12) level and yielded remarkably close agreement with experiment in this …

Fully Differential Cross Sections For Electron-Impact Excitation-Ionization Of Aligned D₂, Esam Ali, A. L. Harris, J. Lower, E. Weigold, Chuang-Gang Ning, Don H. Madison

Physics Faculty Research & Creative Works

We examine fully differential cross sections for 176 eV electron-impact dissociative excitation-ionization of orientated D2 for transitions to final ion states 2sσ_g, 2pσ_u, and 2pπ_u. In previous work [Phys. Rev. A 88, 062705 (2013)PLRAAN1050-294710.1103/PhysRevA.88.062705], we calculated these cross sections using the molecular four-body distorted wave (M4DW) method with the ground-state D2 wave function being approximated by a product of two Dyson 1s-type orbitals. The theoretical results were compared with experimental measurements for five different orientations of the target molecule (four in the scattering plane and one perpendicular to the scattering plane). For the unresolved …

Rydberg Time-Of-Flight And Imaging Probes Of The Velocity-Dependent Hydrogen Atom Spin Polarization, Bernadette Michlewicz Broderick

Wayne State University Dissertations

Insights into electron spin and nuclei are central to the field of chemical reaction dynamics. Of particular note is the study of spin-polarized hydrogen (SPH) atoms, which result from photodissociation of molecules. Examination of the detailed H-atom spin polarization is achieved by determining the projection of the electron spin onto the probe laser direction. In doing so, its angular distribution, complex dissociation pathways, and coherent excitation mechanisms may be revealed. Approaches to detect SPH atoms are experimentally challenging due to the difficulty associated with probing ground-state H atoms through isolated fine structure levels, which is the only direct way to …

Projectile Coherence Effects In Electron Capture By Protons Colliding With H₂ And He, Sachin D. Sharma, Ahmad Hasan, Kisra N. Egodapitiya, T. P. Arthanayaka, G. Sakhelashvili, Michael Schulz

Physics Faculty Research & Creative Works

We have measured differential cross sections for single and dissociative capture for 25 and 75 keV protons colliding with H₂ and He. Significant differences were found depending on whether the projectile beam was coherent or incoherent. For 75 keV p+H₂ these differences can be mostly associated with molecular two-center interference and possibly some contributions from path interference. For 25 keV (both targets) they are mostly due to path interference between different impact parameters leading to the same scattering angles and, for the H₂ target, possibly some contributions from molecular two-center interference.

Astrochemical Dynamics: Fundamental Studies Relevant To Titan's Atmosphere, Wilson Kamundia Gichuhi

Wayne State University Dissertations

This work presents results of primary fundamental photodissociation and state-specific ion-molecule dynamical studies that are relevant to understanding the formation and growth mechanisms of unsaturated hydrocarbon molecules, haze layers and aerosols in Titan's upper atmosphere. In the diacetylene dimer, it is shown, via laboratory studies combined with electronic structure calculations that the photodissociation of the dimer readily initiates atomic hydrogen (H) loss and atomic H transfer reactions forming two prototypes of resonantly stabilized free radicals, C8H3 and C4H3, respectively. In ethylamine cation, high-level ab initio calculations identify the complex dissociation pathways for the ground state CH3CH2NH2+ radical cation at 233.3 …

Photodissociation Dynamics In Titan's Atmosphere, Welvidanalage Ruchira Silva

Wayne State University Dissertations

Photodissociation dynamics of molecules relevant to understanding Titan's atmosphere (diacetylene, cyanoacetylene and heptane isomers) are carried out under collisionless condition using the DC slice imaging technique. In diacetylene photodissociation, two-photon processes dominate at 243 nm and 212 nm whereas at 121.6 nm, a one-photon dissociation process dominates. Direct measurement of the lifetime of metastable triplet diacetylene confirms sub-microsecond lifetimes. Photodissociation of cyanoacetylene at 193.3 nm proceeds on the S1 potential energy surface with an exit barrier. In heptane photodissociation, the dissociation occurs on the ground state or low-lying triplet states with nonradiative electronic relaxation. Time-of-flight mass spectroscopy studies in this …

Electronic Spectroscopy And Dissociation Dynamics Of Gasphase Transition Metal Containing Cations And Dications, Kanchana Manori Perera

Doctoral Dissertations 1896 - February 2014

Studies of gas-phase ionic clusters have become an integral component in understanding microsolvation and catalysis by transition metal cations. Further interest in this field is due to the possibility of bridging the gap between the condensed and gas phases by developing our understanding of clusters and the possibility that small clusters can have unique chemical and catalytic properties. Most gas phase studies have focused on singly charged ions. Electrospray allows for the production of multiply charged ions solvated by a few solvent molecules. Understanding smaller reactive species such as metal centered clusters with well-defined, gas phase conditions also allows for …

Energy Conserving Approximations To The Quantum Potential: Dynamics With Linearized Quantum Force, Sophya Garashchuk, Vitaly A. Rassolov

Faculty Publications

Solution of the Schrödinger equation within the de Broglie–Bohm formulation is based on propagation of trajectories in the presence of a nonlocal quantum potential. We present a new strategy for defining approximate quantum potentials within a restricted trial function by performing the optimal fit to the log-derivatives of the wave function density. This procedure results in the energy-conserving dynamics for a closed system. For one particular form of the trial function leading to the linear quantum force, the optimization problem is solved analytically in terms of the first and second moments of the weighted trajectory distribution. This approach gives exact …

Neutral Dissociation Of Hydrogen Following Photoexcitation Of Hcl At The Chlorine K Edge, D. L. Hansen, J. Cotter, G. R. Fisher, K. T. Leung, R. Martin, Paul Neill, Rupert C. Perera, I. A. Sellin, Marc Simon, Y. Uehara, B. Vanderford, S. B. Whitfield

Chemistry and Biochemistry Faculty Research

Time-of-flight mass spectroscopy was used to study the relaxation dynamics of HCl following photoexcitation in the vicinity of the Cl K edge (~2.8 keV) using monochromatic synchrotron radiation. At the lowest resonant excitation to the 6ơ* antibonding orbital, almost half of the excited molecules decay by emission of a neutral H atom, mostly in coincidence with a highly charged Cln1 ion. The present work demonstrates that neutral-atom emission can be a significant decay channel for excited states with very short lifetimes (1 fs). [S1050-2947(98)03604-X]

Investigation Of Alignment Dynamics In Mg-Ne And Mg-Ar Two-Photon Fractional Collisions, David Allen Olsgaard

Physics Theses & Dissertations

A new technique is used to observe the dynamics of electronic alignment in a dissociating collision complex. The technique requires the absorption of two optical photons during a single binary collision. Two exciting light fields are tuned into the wings of the 3s¹s₀-3p₁ and 3p¹p₁-5s¹s₀ resonances of Mg where strong collisions with rare gas atoms induce transitions between corresponding molecular states. The alignment produced in the intermediate state by the first excitation is probed by the second laser as a function of relative linear laser polarization and laser …

Photodissociation Of Co In The Thermosphere Of Venus, Jane L. Fox

Physics Faculty Publications

Recent investigations of CO photoabsorption demonstrate that photodissociation longward of the ionization threshold at 88.5 nm occurs primarily through line absorptions rather than continuous processes. We have constructed high resolution photoabsorption cross sections for CO at rotational temperatures near 250 K from the improved data on dissociating transitions. We examine the effects of the new cross sections on the rate of solar photodissociation of CO in the thermosphere of Venus and compare the results to values obtained with the lower resolution cross sections available previously. We find that the photodissociation profile peaks slightly higher in the atmosphere and the peak …

Expansion Approach To Photodissociation Dynamics. I. Theory, Kazuo Takatsuka, Mark S. Gordon

Mark S. Gordon

We propose a new formulation for a photodissociation process to which an expansional (or algebraic) quantum‐variation‐method of scattering is applicable. By solving a ’’full collision’’ problem which describes a multichannel process on the repulsive surface, the photodissociation scheme takes account of interchannel coupling from the outset. Our expression for the amplitude of the partial linewidth is similar to that of the ’’half‐collision’’ approximation of Jortner e t a l. The present formalism differs in that the scattering wave functions take acount of interchannel coupling exactly. As a result, only on‐the‐energy‐shell contributions appear in the partial linewidth.

Expansion Approach To Photodissociation Dynamics. Ii. Correction Formula For Linewidth And Numerical Examples For Hcn, Kazuo Takatsuka, Mark S. Gordon

Mark S. Gordon

A correction formula for energy disposal and linewidth of photodissociation dynamics is proposed. This formula was derived from an identity similar to the Kato identity of the scattering theory. Thanks to the correction formula the resultant linewidth turns out to be more accurate and stable even when a relatively poor basis set is used. Numerical examples for assumed direct dissociation of HCN, DCN, and TCN and for the predissociation of HCN and DCN are presented.