Quantum Master Equations for Simulating Chemical Dynamics

用于模拟化学动力学的量子主方程

• 批准号: 2154114
• 负责人: Eitan Geva
• 金额: $ 48万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-05-01 至 2025-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154114&HistoricalAwards=false
• 关键词: Quantum; Master; Equations; Simulating; Chemical

Professor Eitan Geva of the University of Michigan is supported by an award from the Chemical Theory, Models and Computational Methods (CTMC) program in the Division of Chemistry to develop a new general purpose cost-effective and efficient methodology that will enable computer simulations of the chemical dynamics underlying technologically and biologically important processes, such as photosynthesis, photovoltaics and nanoelectronics. The new methodology aims at closing the gap between theory and experiment, by focusing on measurable quantities and reducing the inputs to the minimum required in order to understand how those measurable quantities change over time. In addition, Eitan Geva will also advance a novel Compute-to-Learn (C2L) pedagogy, which is based on a peer-led honors studio where undergraduate students work collaboratively to create public-domain interactive computer demos that demonstrate physical chemistry concepts. With above 50% female enrollment, the C2L pedagogy is a model for how to make teaching programming inclusive. Eitan Geva and his group will develop and benchmark new types of generalized quantum master equations that allow for much greater flexibility than is currently available with respect to the electronic observables of interest and their dimensionality, thereby giving rise to more streamlined, cost-effective and efficient implementations. Each generalized quantum master equation corresponds to the exact equation of motion for the electronic observable it is derived for. Within those equations, the effect of projected-out degrees of freedom is given in terms of compact memory kernels and inhomogeneous terms, which can be obtained from projection-free inputs by solving Volterra equations. Computational protocols are developed for calculating the projection-free inputs for all-atom models of chemical condensed-phase systems via either mapping onto harmonic models and using quantum-mechanically exact methods or using quasiclassical methods based on combining the linearized semiclassical approximation with the mapping Hamiltonian framework. In addition, multiple new perturbative quantum master equations that mirror the multitude of non-perturbative generalized quantum master equations are developed, as well as protocols for calculating the corresponding perturbative memory kernels via the same methods used for calculating the projection-free inputs. The quantum master equations developed will be applied to and tested on new benchmark models, all-atom models and polaritonic chemistry models. The potential of using initial state entanglement to achieve quantum control of chemical dynamics is also investigated.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教授得到了化学系化学理论，模型和计算方法（CTMC）计划的支持，以开发一种新的通用成本效益和有效的方法，该方法将使计算机模拟技术和生物学重要过程的化学动力学，如光合作用，光化学和纳米电子学。 新方法的目的是缩小理论与实验之间的差距，方法是侧重于可测量的数量，并将投入减少到所需的最低限度，以便了解这些可测量的数量如何随着时间的推移而变化。此外，Eitan Geva还将推进一种新颖的计算学习（C2L）教学法，该教学法基于同行领导的荣誉工作室，本科生在该工作室中合作创建公共领域的交互式计算机演示，展示物理化学概念。女性入学率超过50%，C2L教学法是如何使教学方案具有包容性的模式。Eitan Geva和他的团队将开发和基准测试新类型的广义量子主方程，这些方程在感兴趣的电子观测量及其维度方面具有比目前更大的灵活性，从而产生更精简，更具成本效益和效率的实现。每个广义量子主方程对应于它所导出的电子可观测量的精确运动方程。在这些方程中，投影出的自由度的效果给出了紧凑的内存内核和非齐次项，这可以通过求解沃尔泰拉方程从投影自由输入获得。计算协议开发用于计算投影自由输入的化学凝聚相系统的全原子模型，通过映射到谐波模型和使用量子力学精确方法或使用准经典方法的基础上结合的线性化半经典近似与映射哈密顿框架。此外，开发了反映大量非微扰广义量子主方程的多个新的微扰量子主方程，以及用于通过用于计算无投影输入的相同方法来计算对应的微扰存储器内核的协议。所开发的量子主方程将应用于新的基准模型、全原子模型和极化子化学模型并进行测试。该奖项反映了NSF的法定使命，并通过使用基金会的智力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

Cavity-Modified Fermi’s Golden Rule Rate Constants from Cavity-Free Inputs

来自无腔输入的腔体修正费米黄金法则速率常数

• DOI: 10.1021/acs.jpcc.2c08996
• 发表时间: 2023
• 期刊: The Journal of Physical Chemistry C
• 作者: Saller, Maximilian A.;Lai, Yifan;Geva, Eitan
• 通讯作者: Geva, Eitan

A Computational Study of the Electronic Energy and Charge Transfer Rates and Pathways in the Tetraphenyldibenzoperiflanthene/Fullerene Interfacial Dyad

四苯基二苯并葘弗兰烯/富勒烯界面二元组中电子能量和电荷转移速率和路径的计算研究

• DOI: 10.1021/acs.jpclett.3c01927
• 发表时间: 2023
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Schubert, Alexander;Bhandari, Srijana;Geva, Eitan;Dunietz, Barry D.
• 通讯作者: Dunietz, Barry D.

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

Cavity-modified Fermi’s golden rule rate constants: Beyond the single mode approximation

腔体修正费米黄金法则速率常数：超越单模近似

• DOI: 10.1063/5.0172265
• 发表时间: 2023
• 期刊: The Journal of Chemical Physics
• 作者: Saller, Maximlian A.;Lai, Yifan;Geva, Eitan
• 通讯作者: Geva, Eitan