Quantum Simulation of Chemical Dynamics in Solution

溶液中化学动力学的量子模拟

• 批准号: 0134775
• 负责人: Peter Rossky
• 金额: $ 42.42万
• 依托单位: University of Texas at Austin
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-01-01 至 2005-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0134775&HistoricalAwards=false
• 关键词: Quantum; Simulation; Chemical; Dynamics; Solution

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.

德克萨斯大学奥斯汀分校的Peter Rossky在理论和计算化学项目的支持下开展了一项研究，该研究解决了模拟方法的发展和应用，以描述凝聚态中的非绝热化学过程，强调了液体环境中的电子过程。该计划包括一个平衡的方法发展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，分子内电子转移的非绝热电子动力学将通过直接模拟来探索，以研究分子内和溶剂动力学对速率、光谱和电子耦合的影响，电子结构的环境依赖性，以及非平衡初始条件的作用。接下来，将开发和实施完全详细的溶剂化电子和分子内电荷转移系统的两态/谐波浴模型，允许对简化描述和理论算法进行相当严格的验证，并使对分子化学动力学的新见解成为可能。最后，将为原子非绝热模拟开发新的理论和算法，包括环境诱导的电子量子相干衰减的替代描述和实现耗散量子动力学模拟的替代算法。这一努力的结果有望揭示感兴趣的单个化学例子的机制特征，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的液体或固体中，包括那些负责生物功能和合成材料性能的反应。该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。相关实验方法的持续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、生物过程（如光合作用）和发生在液相光化学中的化学过程的模型的理解和预测能力。