Quantum Simulation of Chemical Dynamics in Solution

Peter Rossky得到了理论和计算化学计划的资助，继续他在溶液中化学动力学的量子模拟领域的工作。本研究侧重于描述溶液中化学过程的混合量子模拟方法和经典力学模拟方法的发展和应用。重点研究了非绝热量子动力学的模拟。这项工作将涉及：1)与溶液中溶质激发电子态的非辐射弛豫有关的溶剂模的基本分子水平描述；2)量子非绝热模拟算法在分子光电离动力学和水和非水溶液中分子内电荷转移动力学中的新应用；3)非绝热量子动力学新算法的发展和实现；以及4)现有非绝热算法的推广和测试，重点分析量子相干性在凝聚相所得结果中的作用。大多数化学反应发生在溶液中。这一事实激发了一项巨大的研究努力，以阐明一套描述液体中化学动力学的统一原理。为了充分解决这一问题，需要详细了解化学事件过程中发生的分子运动以及溶质内部和溶质与溶剂之间的能量流动。最近在澄清这些方面方面取得了不同寻常的进展。激光技术的进步使在基本事件的时间尺度上直接实验测量化学系统的动力学行为成为可能。同时，在描述溶液化学的理论方法和模型方面也取得了重大进展。Rossky在开发新的计算算法方面的研究将允许通过这些新的实验技术在时间尺度上对现象进行经典和量子力学动力学模拟。

Peter Rossky is supported by a grant from the Theoretical and Computational Chemistry Program to continue his work in the area of quantum simulation of chemical dynamics in solution. This research focuses on both the development and application of mixed quantum and classical mechanical simulation methods for the description of chemical processes in solution. Emphasis is placed on the simulation of nonadiabatic quantum dynamics. The work will address in detail: 1) The fundamental molecular level description of the solvent modes associated with the non-radiative relaxation of solute excited electronic states in liquid solution; 2) New applications of algorithms for quantum nonadiabatic simulation to the dynamics of molecular photoionization and to intramolecular charge transfer dynamics in both aqueous and non-aqueous solution; 3) The development and implementation of new algorithms for nonadiabatic quantum dynamics; and 4) Generalization and testing of current nonadiabatic algorithms with emphasis on an analysis of the role of quantum coherence in the results obtained in the condensed phase. The majority of chemical reactions occur in solution. This fact has stimulated a tremendous research effort to elucidate a set of unifying principles describing chemical dynamics in liquids. To fully address this issue requires a detailed understanding of both the molecular motions that occur during the course of a chemical event and the energy flow within the solute and between the solute and the solvent. Exceptional recent progress in clarifying these aspects has been made. Advances in laser technology enable direct experimental measurement of dynamical behavior of chemical systems on the time scale of the fundamental events. At the same time, significant advances have been made in theoretical methods and models used in describing solution chemistry. Rossky's research in the development of new computational algorithms will allow for both cl assical and quantum mechanical dynamical simulations of phenomena on time scales accessible by these new experimental techniques.