Reaction Dynamics in Molecular Cluster Ions

罗伯特·帕森斯在理论和计算化学项目的支持下，从理论上研究簇离子的复杂动力学。他使用团簇来发现溶剂化、电子转移和能量耗散的微观细节，这些细节将缩合相中的反应与它们的气相类似物区分开来。项目包括羰基硫化物簇中碘阴离子光解的分子动力学模拟，模拟时间分辨光电子谱的更严格处理，以及结合溶剂蒸发的振动弛豫动力学理论的发展。气相的分子离子可以被周围的中性分子溶解，就像水溶液中的离子被水溶解一样。本研究通过增加我们对团簇动力学的理解，建立了与凝聚相现象的联系。特别是，强的和长期的溶质-溶剂相互作用的作用迄今尚未被详细研究。帕森对层次模型的使用在描述这些现象的简单描述的可能局限性方面特别有价值。

Robert Parsons is supported by the Theoretical and Computational Chemistry Program to theoretically investigate complex dynamics in cluster ions. He uses clusters to discover the microscopic details of solvation, electron transfer, and energy dissipation that distinguish reactions in the condensed phase from their gas-phase analogs. Projects include molecular dynamics simulations of iodine anion photodissociation in carbonyl sulfide clusters, a more rigorous treatment of simulated time-resolved photoelectron spectra, and development of a kinetic theory of vibrational relaxation incorporating solvent evaporation.Molecular ions in the gas-phase can become solvated by surrounding neutral molecules in much the same way as ions become solvated by water in aqueous solutions. This research establishes connections to condensed phase phenomena by increasing our understanding of cluster dynamics. In particular, the role of strong and long-ranged solute-solvent interactions has not heretofore been investigated in detail. Parson's use of hierarchical models is particularly valuable in delineating the possible limitations of simpler descriptions of these phenomena.