使用截断的莱布尼兹公式和混合参考自旋翻转时间相关的密度泛函理论快速准确地计算非绝热耦合矩阵元素,The Journal of Physical Chemistry Letters

当前位置： X-MOL 学术 › J. Phys. Chem. Lett. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

使用截断的莱布尼兹公式和混合参考自旋翻转时间相关的密度泛函理论快速准确地计算非绝热耦合矩阵元素
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2021-05-13 , DOI: 10.1021/acs.jpclett.1c00932
Seunghoon Lee ₁ , Yevhen Horbatenko ₂ , Michael Filatov ₂ , Cheol Ho Choi ₂

Affiliation

我们提出了一种快速，准确的数值算法，用于计算一阶非绝热耦合矩阵元素（NACME）。该算法在有限差分方法中采用了截断的Leibniz公式（TLF）逼近，因此可以轻松地与任何基于波动函数的方法结合使用。在这项工作中，我们将算法与最近开发的混合参考自旋翻转时间相关的密度泛函理论（MRSF-TDDFT，为简便起见，MRSF）结合使用。评估了NACME在解离氢分子的单重态电子态之间的准确性。结果表明，中间近似TLF（1）的数值误差可忽略不计，约为^{10 –10}au，同时可以快速计算NACME。由于MRSF方法对所有涉及的电子态都能正确描述H ₂的解离曲线，因此TLF（1）/ MRSF NACME数值与通过完全配置相互作用获得的参考分析值极为吻合。对于多原子分子，MRSF NAC载体与MRCISD NAC载体非常接近。因此，提出的协议是评估NACME的有前途的工具。

"点击查看英文标题和摘要"

Fast and Accurate Computation of Nonadiabatic Coupling Matrix Elements Using the Truncated Leibniz Formula and Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory

We present a fast and accurate numerical algorithm for computing the first-order nonadiabatic coupling matrix element (NACME). The algorithm employs the truncated Leibniz formula (TLF) approximation within the finite-difference method, which makes it easily applicable in connection with any wave function-based methodology. In this work, we used the algorithm in connection with the recently developed mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT, MRSF for brevity). The accuracy is assessed for NACME between the singlet electronic states of a dissociating hydrogen molecule. It is demonstrated that an intermediate approximation, TLF(1), affords a negligible numeric error on the order of ∼10^–10 a.u. while enabling a fast computation of NACME. As the MRSF method yields the correct description of the dissociation curves of H₂ for all the electronic states involved, the numeric TLF(1)/MRSF NACME values are in excellent agreement with the reference analytical values obtained by the full configuration interaction. For polyatomic molecules, the MRSF NAC vectors agree very closely with the MRCISD NAC vectors. Hence, the proposed protocol is a promising tool for the evaluation of NACMEs.

更新日期：2021-05-20

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南