Effective Computation of Coupling Force Constants: Metal Carbonyls as a Test Case

IF 5.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Chemical Theory and Computation Pub Date : 2025-09-10 DOI:10.1021/acs.jctc.5c00645

Henrik Borgman, , , Somi Vasisth, , and , Jörg Grunenberg*,

引用次数: 0

Abstract

An automated protocol enabling the efficient computation of unique potential coupling constants is presented. Several modern density functional (DFT) methods are tested against coupled cluster theory (CCSD(T)) in order to evaluate their quality in producing reliable compliance matrix off-diagonal elements. While force coupling constants could serve as descriptors of electron delocalization in general, we tested the ability of coupling compliance constants as descriptors of the Dewar–Chatt–Duncanson model in VCO^–, CrCO, MnCO⁺, FeCO²⁺, NiCO, CuCO⁺, FeCO⁺ and the isoelectronic hexacarbonyls of the 3d and 5d series from Ti to Co, and Hf to Ir, respectively. A robust semiautomated algorithm including the computation of all compliance coupling constants as inverse covariant second derivatives is implemented in our open source version of the COMPLIANCE code.

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耦合力常数的有效计算：以金属羰基为例。

提出了一种能够有效计算唯一电位耦合常数的自动化协议。针对耦合聚类理论（CCSD(T)）对几种现代密度泛函（DFT）方法进行了测试，以评价它们在生成可靠的柔度矩阵非对角元方面的质量。虽然力耦合常数通常可以作为电子离域的描述符，但我们在VCO-、CrCO、MnCO+、FeCO2+、NiCO、CuCO+、FeCO+以及从Ti到Co和Hf到Ir的3d和5d系列等电子六羰基中分别测试了耦合顺性常数作为dewar - hat - duncanson模型描述符的能力。在我们的开源版本的合规代码中实现了一个鲁棒的半自动算法，该算法包括将所有合规耦合常数作为逆协变二阶导数的计算。

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Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere.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