Non-adiabatic Couplings in Surface Hopping with Tight Binding Density Functional Theory: The Case of Molecular Motors.

IF 5.7 1区 化学 Q2 CHEMISTRY, PHYSICAL
Gonzalo Díaz Mirón, Carlos R Lien-Medrano, Debarshi Banerjee, Marta Monti, Bálint Aradi, Michael A Sentef, Thomas A Niehaus, Ali Hassanali
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引用次数: 0

Abstract

Nonadiabatic molecular dynamics (NAMD) has become an essential computational technique for studying the photophysical relaxation of molecular systems after light absorption. These phenomena require approximations that go beyond the Born-Oppenheimer approximation, and the accuracy of the results heavily depends on the electronic structure theory employed. Sophisticated electronic methods, however, make these techniques computationally expensive, even for medium size systems. Consequently, simulations are often performed on simplified models to interpret the experimental results. In this context, a variety of techniques have been developed to perform NAMD using approximate methods, particularly density functional tight binding (DFTB). Despite the use of these techniques on large systems, where ab initio methods are computationally prohibitive, a comprehensive validation has been lacking. In this work, we present a new implementation of trajectory surface hopping combined with DFTB, utilizing nonadiabatic coupling vectors. We selected the methaniminium cation and furan systems for validation, providing an exhaustive comparison with the higher-level electronic structure methods. As a case study, we simulated a system from the class of molecular motors, which has been extensively studied experimentally but remains challenging to simulate with ab initio methods due to its inherent complexity. Our approach effectively captures the key photophysical mechanism of dihedral rotation after the absorption of light. Additionally, we successfully reproduced the transition from the bright to dark states observed in the time-dependent fluorescence experiments, providing valuable insights into this critical part of the photophysical behavior in molecular motors.

紧密结合密度泛函理论表面跳变中的非绝热耦合:分子马达案例。
非绝热分子动力学(NAMD)已成为研究光吸收后分子体系光物理弛豫的重要计算技术。这些现象需要超越玻恩-奥本海默近似的近似值,而结果的准确性在很大程度上取决于所采用的电子结构理论。然而,复杂的电子方法使得这些技术的计算成本高昂,即使是中等规模的系统也不例外。因此,通常需要在简化模型上进行模拟,以解释实验结果。在这种情况下,人们开发了多种技术,使用近似方法,特别是密度泛函紧密结合(DFTB)来执行 NAMD。尽管这些技术可用于计算成本高昂的大型系统,但一直缺乏全面的验证。在这项研究中,我们利用非绝热耦合矢量,提出了轨迹表面跳变与 DFTB 结合的新实施方案。我们选择了甲亚胺阳离子和呋喃系统进行验证,与更高层次的电子结构方法进行了详尽的比较。作为案例研究,我们模拟了分子马达类系统,该系统已得到广泛的实验研究,但由于其固有的复杂性,用非线性方法进行模拟仍具有挑战性。我们的方法有效地捕捉到了光吸收后二面旋转的关键光物理机制。此外,我们成功地再现了在随时间变化的荧光实验中观察到的从亮态到暗态的转变,为了解分子马达光物理行为的这一关键部分提供了宝贵的见解。
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来源期刊
Journal of Chemical Theory and Computation
Journal of Chemical Theory and Computation 化学-物理:原子、分子和化学物理
CiteScore
9.90
自引率
16.40%
发文量
568
审稿时长
1 months
期刊介绍: The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.
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