Theory and Application of Some New Approaches to Electronically Non-Adiabatic Dynamic

电子非绝热动力学一些新方法的理论与应用

• 批准号: 1856707
• 负责人: William Miller
• 金额: $ 36万
• 依托单位: University of California-Berkeley
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1856707&HistoricalAwards=false
• 关键词: Theory; Application; Some; New; Approaches

William H. Miller and Stephen J. Cotton of the University of California, Berkeley are supported by an award from the Chemical Theory, Models and Computational Chemistry Program in the Division of chemistry to develop theoretical methods for simulating a variety of molecular processes that are fundamental to many modern technologies. These processes involve coupled electronic states. Such simulations allow researchers to understand these processes more deeply and thus be able to modify them in useful ways. Examples are biomolecular processes, photovoltaic behavior, and photo-catalysis. The approach that Miller and Cotton is developing is characterized by its simplicity and its efficiency. The goal is to have a reliable and easy to use approach for simulating larger and more complex molecular systems than is what is currently possible. The specific focus of this research is electronically non-adiabatic processes, i.e., those that involve transitions between different electronic states. The challenge is to treat the electronic degrees of freedom and the nuclear degrees of freedom, to which they are coupled, in a consistent framework. The approach uses the Meyer-Miller (MM) model for the electronic degrees of freedom, which shows how they can be "mapped" onto harmonic oscillators, one for each electronic state. This then allows the use of classical molecular dynamics for electronics as well as nuclear degrees of freedom. The MM model would be exact if all the degrees of freedom were treated quantum mechanically. Treating them all classically is an approximation but can often be very accurate by using semiclassical ideas to "re-quantize" the electronic degrees of freedom This has resulted in the development of a striking simple symmetrical quasi-classical (SQC) windowing procedure that provides a semiclassical-like "quantization" of the electronic oscillator degrees-of- freedom (DOF) in classical Meyer-Miller (MM) vibronic dynamics. Significant benchmarking of this SQC/MM approach has been seen to give semiclassical-like (and therefore quantum-like) results, but to do so orders of magnitude more efficiently than a true semiclassical calculation and, of course, without the inherent exponentially scaling cost of a full quantum dynamics simulationThis 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.

William H.加州大学伯克利分校的米勒和斯蒂芬·J·科顿获得了化学系化学理论、模型和计算化学项目的奖项，以开发模拟各种分子过程的理论方法，这些过程是许多现代技术的基础。 这些过程涉及耦合的电子状态。 这种模拟使研究人员能够更深入地了解这些过程，从而能够以有用的方式修改它们。 例子是生物分子过程、光伏行为和光催化。米勒和科顿正在开发的方法的特点是简单而有效。 我们的目标是有一个可靠的和易于使用的方法来模拟更大和更复杂的分子系统比目前可能的。这项研究的具体重点是电子非绝热过程，即，涉及不同电子状态之间的跃迁的那些。挑战在于在一个一致的框架中处理电子自由度和核自由度，它们与之耦合。 该方法使用迈耶-米勒（MM）模型的电子自由度，这表明他们如何可以“映射”到谐振子，一个为每个电子状态。这就允许使用经典分子动力学的电子以及核自由度。 如果所有的自由度都用量子力学的方法处理，MM模型将是精确的。 经典地处理它们是一种近似，但通过使用半经典的思想来“重新定义”电子自由度通常可以非常准确。这导致了一个惊人的简单对称准经典（SQC）窗口程序的发展，该程序提供了经典迈耶-米勒（MM）振动动力学中电子振荡器自由度（DOF）的半经典“量子化”。这种SQC/MM方法的重要基准已经被认为给出了半经典的（因此类似量子）的结果，但这样做的数量级更有效地比一个真正的半经典计算，当然，该奖项反映了NSF的法定使命，并被认为是值得通过使用基金会的智力价值进行评估来支持的和更广泛的影响审查标准。

项目成果

The symmetric quasi-classical model using on-the-fly time-dependent density functional theory within the Tamm–Dancoff approximation

• DOI: 10.1080/00268976.2022.2153761
• 发表时间: 2022-09
• 期刊: Molecular Physics
• 影响因子: 1.7
• 作者: J. Talbot;M. Head‐Gordon;Stephen J. Cotton

Dynamic signatures of electronically nonadiabatic coupling in sodium hydride: a rigorous test for the symmetric quasi-classical model applied to realistic, ab initio electronic states in the adiabatic representation

氢化钠中电子非绝热耦合的动态特征：对应用于绝热表示中的真实从头电子态的对称准经典模型的严格测试

• DOI: 10.1039/d1cp04090a
• 发表时间: 2022
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Talbot, Justin J.;Head-Gordon, Martin;Miller, William H.;Cotton, Stephen J.
• 通讯作者: Cotton, Stephen J.