Theses and Dissertations at Montana State University (MSU)
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Item Reactive-atom scattering dynamics and liquid-vacuum interfacial structure(Montana State University - Bozeman, College of Letters & Science, 2019) Smoll, Eric James, Jr.; Chairperson, Graduate Committee: Timothy Minton; Maria Tesa-Serrate, Timothy K. Minton and Kenneth G. McKendrick were also authors of the article, 'Review of atomic and molecular collisions at liquid surfaces' in the journal 'Annual review of physical chemistry' which is contained within this dissertation.; Simon M. Purcell, Lucia D'Andrea, John M. Slattery, Duncan W. Bruce, Matthew L. Costen, Kenneth G. McKendrick and Timothy K. Minton were co-authors of the article, 'Probing conformational heterogeneity at the ionic liquid-vacuum interface by reactive atom scattering' in the journal 'The Journal of Physical Chemistry Letters' which is contained within this dissertation.; Timothy K. Minton was an author of the article, 'Scattering-angle randomization in nonthermal gas-liquid collisions' submitted to the journal 'Journal of physical chemistry C' which is contained within this dissertation.; John M. Slattery, Timothy K. Minton were also authors of the article, 'Probing a ruthenium coordination complex at the ionic liquid-vacuum interface with reactive atom scattering, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry' submitted to the journal 'Journal of physical chemistry C' which is contained within this dissertation.Experiments to characterize reactive and nonreactive gas-liquid scattering dynamics were carried out with the use of a crossed molecular beams apparatus configured for beam-surface scattering. In each experiment, the identity of the gas and liquid was strategically selected to reveal fundamental insights on the relationship between scattering observables and liquid-vacuum interfacial structure. This work is crucially important for the experimental advancement of liquid surface science and has the potential to impact our understanding of the chemical role of gas-liquid interfaces in the environment. An extensive literature review suggests that the inherent chemical specificity of reactive scattering is a promising probe of composition at the liquid-vacuum interface. We expand on what has been demonstrated in the literature by exploring F-atom scattering from the liquid-vacuum interface of deuterium labeled variants of the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C 4 mim][Tf 2 N]). The experimental data and new molecular dynamics simulations provide evidence for the extreme surface specificity of reactive scattering and help quantify the relative populations of [C 4mim] + conformations at the liquid-vacuum interface. Also, at a fixed incident angle, the site-specific IS flux angular distributions from [C 4mim] + were discovered to be related by the addition or subtraction of a line-shape proportional to a cos(θf) function. To investigate this phenomenon, a separate study of noble gas scattering from the liquid-vacuum interface of other low vapor pressure liquids was carried out. Our results support the generality of the relative cos(θf) character trend and demonstrate that the relative cos(θf) character between total flux angular distributions from squalane and a perfluoropolyether is independent of gas identity and incident angle suggesting that this metric is an intrinsic property of the liquid pair. The existing evidence suggests that the relative cos(θf) character between flux angular distributions is a result of angle-randomization from multiple collision scattering trajectories induced by atomic-scale corrugation at the liquid-vacuum interface. A study on the liquid-vacuum interface structure of a solution of [RuCl 2(p-cymene)P(C 8H 17) 3] in perdeuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (d 11-[C 2mim][Tf 2N]) is also discussed. The experimental data suggest that [RuCl(p-cymene)P(C 8H 17) 3] + is enriched at the liquid-vacuum interface at the expense of d 11-[C 2mim] + and the hydrocarbon chains of the Ru-complex protrude into the vacuum.Item Gas-surface interactions with sp 2 carbon in extreme environments(Montana State University - Bozeman, College of Letters & Science, 2018) Murray, Vanessa Jean; Chairperson, Graduate Committee: Timothy Minton; Brooks C. Marshall, Philip J. Woodburn and Timothy K. Minton were co-authors of the article, 'Inelastic and reactive scattering dynamics of hyperthermal O and O 2 on hot vitreous carbon surfaces' in the journal 'Journal of physical chemistry C' which is contained within this thesis.; Eric J. Smoll Jr. and Timothy K Minton were co-authors of the article, 'Dynamics of graphite oxidation at high temperature' in the journal 'Journal of physical chemistry C' which is contained within this thesis.; Marcin D. Pilinski, Eric J. Smoll, Jr., Min Qian, Timothy K. Minton, Stojan M. Madzunkov and Murray R. Darrach were co-authors of the article, 'Gas-surface scattering dynamics applied to concentration of gases for mass spectrometry in tenuous atmospheres' in the journal 'Journal of physical chemistry C' which is contained within this thesis.; Neil A. Mehta is an author and Chenbiao Xu, Deborah A. Levin and Timothy K. Minton were co-authors of the article, 'Scattering dynamics of N 2 from highly oriented pyrolytic graphite' in the journal 'Journal of physical chemistry C' which is contained within this thesis.; Chenbiao Xu, Savio Poovatthingal and Timothy K. Minton were co-authors of the article, 'Scattering dynamics of nitromethane and methyl formate on HOPG' submitted to the journal 'Journal of physical chemistry C' which is contained within this thesis.Molecular beam scattering experiments can determine the relative importance of reactive and non-reactive processes that occur when a surface is bombarded with high energy atoms and molecules. The mechanisms by which these processes proceed are inferred by analyzing the angle-resolved flux and energy distributions of the scattered products. The studies presented in this thesis have been conducted with a crossed molecular beams machine reconfigured for surface scattering. Two molecular beam sources were used. One uses a laser detonation process to produce high translational energy O atoms in the ground electronic state, and the other uses a supersonic expansion to produce continuous beams of N 2, nitromethane, or methyl formate. In the first two studies presented in this thesis, the oxidation of dynamics vitreous carbon and highly oriented pyrolytic graphite (HOPG) held at surface temperatures in the range of 800 - 2300 K by O atoms with a translational energy of ~ 500 kJ mol -1 are presented. These two studies revealed that the reactivity is suppressed at high temperature because O atoms desorb from the surface before they react to form CO and CO 2. Even though the translational energy of the O atoms was high, the surface reactions proceeded primarily through reactions that occurred in thermal equilibrium with the surface. The third study focuses on the scattering dynamics of O, O 2, and Ar with the surfaces of a gold thin-film, SiO 2, and HOPG. The results of the experiments were used to evaluate the efficacy of a proposed gas concentrator. The strong forward scattering on the HOPG surface made it the most suitable surface for the gas concentrator. The fourth study examines the non-reactive scattering dynamics of N 2 with HOPG. At high surface temperature, the residence time of N 2 is too short for the molecule to fully accommodate to the surface. Thus, even if the molecule suffers multiple collisions with the surface, it will scatter into the vacuum before it can come into thermal equilibrium with the surface. The results have been used in conjunction with theoretical calculations by a collaborator to investigate the relationship between the potential energy surface and the scattering dynamics. In order determine the usefulness of an HOPG concentrator with complex molecules, the scattering dynamics of methyl formate and nitromethane on HOPG were studied. These molecules do not shatter upon impact with the surface and they both scatter strongly in the forward direction through direct and indirect mechanisms, suggesting that the proposed HOPG concentrator should perform as desired. In all studies described in this thesis, the fundamental gas-surface scattering dynamics were elucidated from molecular beam experiments, and these fundamental results have direct links to modeling the performance of hypersonic vehicles and designing a gas concentrator for mass spectrometry in tenuous atmospheres.