Automatic Differentiation for Explicitly Correlated MP2.

IF 5.7 1区化学 Q2 CHEMISTRY, PHYSICAL Journal of Chemical Theory and Computation Pub Date : 2024-10-08 Epub Date: 2024-09-23 DOI:10.1021/acs.jctc.4c00818

Erica C Mitchell, Justin M Turney, Henry F Schaefer

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Abstract

Automatic differentiation (AD) offers a route to achieve arbitrary-order derivatives of challenging wave function methods without the use of analytic gradients or response theory. Currently, AD has been predominantly used in methods where first- and/or second-order derivatives are available, but it has not been applied to methods lacking available derivatives. The most robust approximation of explicitly correlated MP2, MP2-F12/3C(FIX)+CABS, is one such method. By comparing the results of MP2-F12 computed with AD versus finite-differences, it is shown that (a) optimized geometries match to about 10^-3 Å for bond lengths and a 10^-6 degree for angles, and (b) dipole moments match to about 10^-6 D. Hessians were observed to have poorer agreement with numerical results (10^-5), which is attributed to deficiencies in AD implementations currently. However, it is notable that vibrational frequencies match within 10^-2 cm^-1. The use of AD also allowed the prediction of MP2-F12/3C(FIX)+CABS IR intensities for the first time.

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显式相关 MP2 的自动微分。

自动微分（AD）为具有挑战性的波函数方法提供了实现任意阶导数的途径，而无需使用解析梯度或响应理论。目前，自动微分主要用于一阶和/或二阶导数可用的方法，但尚未应用于缺乏可用导数的方法。显式相关 MP2 的最稳健近似方法 MP2-F12/3C(FIX)+CABS，就是这样一种方法。通过比较用 AD 计算的 MP2-F12 结果与有限差分计算的结果，可以看出：(a) 优化后的几何形状与键长的匹配度约为 10-3 Å，与角度的匹配度约为 10-6 度；(b) 偶极矩与键长的匹配度约为 10-6 D。不过，值得注意的是，振动频率的吻合度在 10-2 cm-1 以内。使用 AD 还首次预测了 MP2-F12/3C(FIX)+CABS 的红外强度。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

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Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere.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.