Quantum Simulation of Chemical Dynamics in Solution

德克萨斯大学奥斯汀分校的Peter Rossky得到了理论和计算化学计划的支持，开展研究，解决模拟方法的开发和应用，以描述凝聚相中的非绝热化学过程，强调液体环境中的电子过程。该计划包括一个平衡的方法来发展的方法和应用这些理论方法的实验研究系统。 该项目将侧重于三个领域。 首先，非绝热电子动力学的分子内电子转移将探索使用直接模拟，研究分子内和溶剂动力学的影响率，光谱和电子耦合，电子结构的环境依赖性，和非平衡初始条件的作用。 接下来，将开发和实施溶剂化电子和分子内电荷转移系统的完全详细的两个状态/谐波浴模型，允许更严格地验证简化的描述和理论算法，以及使分子化学动力学的新见解。 最后，新的理论和算法将开发原子非绝热模拟，包括环境诱导的电子量子相干性衰减的替代描述和实现耗散量子动力学模拟的替代算法。 这项工作的成果有望揭示感兴趣的单个化学实例的机理特征，提高基于模型的实验数据描述的解释能力，并增强应用于日益复杂的系统的理论和建模的预测能力。大多数化学过程发生在冷凝液体或固体中，包括那些负责生物功能和合成材料性能的反应。 本研究项目旨在阐明涉及电子状态变化的化学现象的理论原理。 相关实验方法的不断进步将使理论和实验越来越能够直接相互作用，并有望提高对电致发光材料，光合作用等生物过程以及溶液相光化学中发生的化学过程的模型的理解和预测能力。

Peter Rossky of the University of Texas at Austin is supported by the Theoretical and Computational Chemistry Program to carry out research that addresses the development and application of simulation methods to describe nonadiabatic chemical processes in condensed phases, emphasizing electronic processes in liquid environments. The plan includes a balanced approach to the development of methods and the application of these theoretical methods to experimentally studied systems. The project will focus on three areas. First, non-adiabatic electronic dynamics for intramolecular electron transfer will be explored using direct simulation, to investigate intramolecular and solvent dynamical effects on rates, spectroscopy and electronic coupling, the environmental dependence of electronic structure, and the role of non-equilibrium initial conditions. Next, fully detailed two state/harmonic bath models of solvated electrons and of intramolecular charge transfer systems will be developed and implemented, allowing considerably more rigorous validation of reduced descriptions and of theoretical algorithms, as well as enabling new insights into molecular chemical dynamics. Finally, new theory and algorithms will be developed for atomistic non-adiabatic simulation, including alternative descriptions of environmentally induced electronic quantum coherence decay and alternative algorithms for implementing dissipative quantum dynamics simulation. Outcomes from this effort are expected to reveal the mechanistic character of the individual chemical examples of interest, increase the interpretive capacity of model-based descriptions of experimental data, and enhance the predictive capacity of theory and modeling applied to increasingly complex systems.Most chemical processes occur in a condensed liquid or solid, including those reactions that are responsible for biological function and synthetic materials performance. This research project aims to elucidate theoretical principles underlying chemical phenomena that involve changes in electronic state. Continued advances in related experimental methods will make theory and experiment increasingly able to interact directly, and promise to enhance the understanding and predicted capability of models for electroluminescent materials, biological processes such as photosynthesis, and chemical processes that occur in solution phase photochemistry.