Combining the quasi-classical mapping Hamiltonian approach with the generalized quantum master equation to simulate nonadiabatic molecular dynamics and its spectroscopic signature

将准经典映射哈密顿方法与广义量子主方程相结合来模拟非绝热分子动力学及其光谱特征

• 批准号: 1800325
• 负责人: Eitan Geva
• 金额: $ 46万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2022-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800325&HistoricalAwards=false
• 关键词: Combining; quasi; classical; mapping; Hamiltonian

Eitan Geva of the University of Michigan is supported by an award from the Chemical Theory, Models and Computational Methods program in the Division of Chemistry to develop new theoretical and computational approaches to model and simulate molecular systems involving more than one electronic state. In these systems, some of the electrons are excited. There is coupling between the lowest energy electronic state and higher energy excited states. Chemists refer to the dynamics of these systems as "nonadiabatic" molecular dynamics. Nonadiabatic dynamics are important in biological processes, for example cellular respiration and photosynthesis. They are also important in emerging technologies such as energy storage and photovoltaics. These systems also very difficult to simulate because nonadiabatic dynamics are inherently quantum-mechanical. Truly quantum calculations have a very large computational cost which puts them beyond the reach of even the most advanced currently available computers. Computer simulations of classical molecular dynamics, however, are cost-effective for large and complex molecular systems. The Geva group is developing a methodology for simulating nonadiabatic dynamics accurately and reliably at classical-like computational cost, using what is called a "semiclassical" approach. Dr. Geva is also involved in activities to modernize and improve the physical chemistry curricula and to further develop a new Compute-to-Learn pedagogy.The methodology combines the quasi-classical mapping Hamiltonian approach for modeling the electronically nonadiabatic dynamics of a multi-state molecular system with the generalized quantum master equation, for describing the reduced dynamics of the electronic degrees of freedom, and optical response theory, for calculating nonlinear time-resolved spectral signals. The synthesis of the above-mentioned three components (the quasi-classical mapping Hamiltonian, generalized quantum Master equation and optical response theory) leads to a powerful methodology, which is necessary to bridge the gap between theory and experiment. It does so by allowing one to calculate experimentally relevant quantities like electronic transition rates and nonlinear time-resolved spectral signals in an accurate, cost-effective and self-consistent manner, starting from explicitly molecular models, where the dynamics of the nuclear degrees of freedom is governed by anharmonic electronic-state-specific force fields. Method development takes place in the context of several model systems with increasing level of molecular detail, including two-state donor-acceptor benchmark models, models of photosynthetic reaction centers and models of triads and dyads in liquid solution. It should be noted that the above-mentioned methodology is general and not limited to the systems in the context of which it is being developed. The methods are disseminated broadly via publications, presentations in professional meetings, collaborating with experimental groups and the Software Infrastructure for Sustained Innovation NSF program. Group members receive extensive training that prepares them for an independent career in an academic institution, government lab or industry. This research program also contributes to the university teaching mission via strengthening the relationship between computational and experimental groups, modernizing curricula of physical chemistry courses, and advancing a new Compute-to-Learn pedagogy within a peer-led honors studio where students registered to introductory physical chemistry undergraduate courses create interactive computer demos that demonstrate physical chemistry concepts.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

密歇根大学的Eitan Geva获得了化学系化学理论，模型和计算方法计划的奖项，以开发新的理论和计算方法来建模和模拟涉及多个电子状态的分子系统。在这些系统中，一些电子被激发。在最低能量电子态和较高能量激发态之间存在耦合。化学家将这些系统的动力学称为“非绝热”分子动力学。非绝热动力学在生物过程中很重要，例如细胞呼吸和光合作用。 它们在能源储存和光化学等新兴技术中也很重要。 这些系统也很难模拟，因为非绝热动力学本质上是量子力学的。 真正的量子计算具有非常大的计算成本，即使是目前最先进的计算机也无法实现。 然而，经典分子动力学的计算机模拟对于大型和复杂的分子系统是具有成本效益的。 Geva小组正在开发一种方法，使用所谓的“半经典”方法，以类似经典的计算成本准确可靠地模拟非绝热动力学。 Geva博士还参与了现代化和改进物理化学课程的活动，并进一步开发了新的计算学习教学法。该方法将用于模拟多态分子系统的电子非绝热动力学的准经典映射哈密顿方法与广义量子主方程相结合，用于描述电子自由度的约化动力学，以及光学响应理论，用于计算非线性时间分辨光谱信号。上述三个组成部分（准经典映射哈密顿量、广义量子主方程和光学响应理论）的综合导致了一个强大的方法论，这是弥合理论与实验之间差距所必需的。它通过允许人们以准确，具有成本效益和自洽的方式计算实验相关的量，如电子跃迁速率和非线性时间分辨光谱信号，从明确的分子模型开始，其中核自由度的动力学由非谐电子状态特定力场控制。方法的发展发生在几个模型系统的背景下，越来越多的分子细节，包括两个国家的供体-受体基准模型，光合作用反应中心的模型和模型的三元组和二元组在液体溶液中。应当指出，上述方法是一般性的，并不局限于正在制定的系统。这些方法通过出版物、在专业会议上的演讲、与实验小组的合作以及持续创新软件基础设施NSF计划广泛传播。小组成员接受广泛的培训，为他们在学术机构，政府实验室或行业的独立职业做好准备。该研究项目还通过加强计算和实验小组之间的关系，使物理化学课程现代化，并在同行中推进新的计算学习教学法，领导的荣誉工作室，学生注册介绍物理化学本科课程创建交互式计算机演示，演示物理化学概念。该奖项反映了NSF的法定使命并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Electronic absorption spectra from off-diagonal quantum master equations

非对角量子主方程的电子吸收光谱

• DOI: 10.1063/5.0106888
• 发表时间: 2022
• 期刊: The Journal of Chemical Physics
• 作者: Lai, Yifan;Geva, Eitan
• 通讯作者: Geva, Eitan

Explaining Spectral Asymmetries and Excitonic Characters of the Core Pigment Pairs in the Bacterial Reaction Center Using a Screened Range-Separated Hybrid Functional

• DOI: 10.1021/acs.jpcb.9b07646
• 发表时间: 2019-10-24
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY B
• 影响因子: 3.3
• 作者: Aksu, Huseyin;Schubert, Alexander;Dunietz, Barry D.
• 通讯作者: Dunietz, Barry D.

On the Role of the Special Pair in Photosystems as a Charge Transfer Rectifier

• DOI: 10.1021/acs.jpcb.9b11431
• 发表时间: 2020-03-12
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY B
• 影响因子: 3.3
• 作者: Aksu, Huseyin;Schubert, Alexander;Dunietz, Barry D.
• 通讯作者: Dunietz, Barry D.

Efficient Charge Generation via Hole Transfer in Dilute Organic Donor–Fullerene Blends

通过稀有机供体富勒烯混合物中的空穴转移有效产生电荷

• DOI: 10.1021/acs.jpclett.0c00058
• 发表时间: 2020
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Song, Yin;Schubert, Alexander;Liu, Xiao;Bhandari, Srijana;Forrest, Stephen R.;Dunietz, Barry D.;Geva, Eitan;Ogilvie, Jennifer P.
• 通讯作者: Ogilvie, Jennifer P.

Intersystem Crossing in Tetrapyrrolic Macrocycles. A First-Principles Analysis

• DOI: 10.1021/acs.jpcc.1c03696
• 发表时间: 2021-06-10
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Bhandari, Srijana;Sarkar, Sunandan;Dunietz, Barry D.
• 通讯作者: Dunietz, Barry D.