Li Zhaoyong, Zhang Chaoqun, Shen Yifan, Wang Linjun
Zhejiang Key Laboratory of Excited-State Energy Conversion and Energy Storage, Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States.
J Phys Chem Lett. 2024 Oct 24;15(42):10544-10553. doi: 10.1021/acs.jpclett.4c02557. Epub 2024 Oct 14.
Due to the cuspidal ridges of adiabatic potential energy surfaces (PESs) and singularities of nonadiabatic couplings (NACs), obtaining an analytical expression for the adiabatic Hamiltonian is difficult. Thereby, nonadiabatic dynamics simulations are often carried out on-the-fly, which is time-consuming. This motivates us to construct quasi-diabatic representations, which have smooth PESs and diabatic couplings. In this study, we propose a new quasi-diabatization method based on minimizing derivative couplings (MDC) in a limited configuration space. The boundary conditions are first considered and finally released to obtain the adiabatic-to-diabatic rotation angles and transformation matrices. As demonstrated in representative one- and two-dimensional models and the widely studied linear H molecule, MDC performs significantly better than the direct integration quasi-diabatization approach. In particular, accurate diabatic potential energy matrices have been successfully obtained even when the NACs of all configurations in the considered space are nonnegligible.
由于绝热势能面（PESs）的尖点脊和非绝热耦合（NACs）的奇点，获得绝热哈密顿量的解析表达式很困难。因此，非绝热动力学模拟通常是实时进行的，这很耗时。这促使我们构建具有平滑PESs和 diabatic 耦合的准绝热表示。在本研究中，我们提出了一种基于在有限构型空间中最小化导数耦合（MDC）的新准绝热方法。首先考虑边界条件，最后释放边界条件以获得绝热到 diabatic 的旋转角度和变换矩阵。如在代表性的一维和二维模型以及广泛研究的线性 H 分子中所证明的，MDC 的性能明显优于直接积分准绝热方法。特别是，即使在所考虑空间中所有构型的 NACs 都不可忽略时，也成功获得了精确的 diabatic 势能矩阵。
