He Xin, Cheng Xiangsong, Wu Baihua, Liu Jian
Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
J Phys Chem Lett. 2024 May 23;15(20):5452-5466. doi: 10.1021/acs.jpclett.4c00793. Epub 2024 May 15.
Recent progress on the coordinate-momentum (CPS) formulation of finite-state quantum systems has revealed that the triangle window function approach is an isomorphic representation of the exact population-population correlation function of the two-state system. We use the triangle window (TW) function and the CPS mapping kernel element to formulate a novel useful representation of discrete electronic degrees of freedom (DOFs). When it is employed with nonadiabatic field (NaF) dynamics, a new variant of the NaF approach (i.e., NaF-TW) is proposed. The NaF-TW expression of the population of any adiabatic state is always positive semidefinite. Extensive benchmark tests of model systems in both the condensed phase and gas phase demonstrate that the NaF-TW approach is able to faithfully capture the dynamical interplay between electronic and nuclear DOFs in a broad region, including where the states remain coupled all the time, as well as where the bifurcation characteristic of nuclear motion is important.
有限态量子系统的坐标 - 动量（CPS）表述的最新进展表明，三角形窗函数方法是两态系统精确布居 - 布居关联函数的同构表示。我们使用三角形窗（TW）函数和CPS映射核元素来构建离散电子自由度（DOF）的一种新颖且有用的表示。当将其应用于非绝热场（NaF）动力学时，提出了NaF方法的一种新变体（即NaF - TW）。任何绝热态布居的NaF - TW表达式始终是半正定的。对凝聚相和气相模型系统进行的广泛基准测试表明，NaF - TW方法能够在很宽的区域内忠实地捕捉电子和核自由度之间的动力学相互作用，包括态始终保持耦合的区域，以及核运动的分叉特征很重要的区域。
