Chemical Bond Overlap Descriptors From Multiconfiguration Wavefunctions

IF 3.4 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Journal of Computational Chemistry Pub Date : 2024-11-28 DOI:10.1002/jcc.27534
Carlos V. Santos-Jr, Elfi Kraka, Renaldo T. Moura Jr
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Abstract

The chemical bond is a fundamental concept in chemistry, and various models and descriptors have evolved since the advent of quantum mechanics. This study extends the overlap density and its topological descriptors (OP/TOP) to multiconfigurational wavefunctions. We discuss a comparative analysis of OP/TOP descriptors using CASSCF and DCD-CAS(2) wavefunctions for a diverse range of molecular systems, including X–O bonds in X–OH (XH, Li, Na, H2B, H3C, H2N, HO, F) and Li–X′ (XF, Cl, and Br). Results show that OP/TOP aligns with bonding models like the quantum theory of atoms in molecules (QTAIM) and local vibrational modes theory, revealing insights such as overlap densities shifting towards the more electronegative atom in polar bonds. The Li–F dissociation profile using OP/TOP descriptors demonstrated sensitivity to ionic/neutral inversion during Li–F dissociation, highlighting their potential for elucidating complex bond phenomena and offering new avenues for understanding multiconfigurational chemical bond dynamics.

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多配置波函数的化学键重叠描述符
化学键是化学中的一个基本概念,自量子力学问世以来,各种模型和描述符不断发展。本研究将重叠密度及其拓扑描述符(OP/TOP)扩展到多配置波函数。我们讨论了使用 CASSCF 和 DCD-CAS(2)波函数对 OP/TOP 描述因子进行比较分析的各种分子体系,包括 X-OH (XH, Li, Na, H2B, H3C, H2N, HO, F) 和 Li-X' (XF, Cl 和 Br) 中的 X-O 键。结果表明,OP/TOP 与分子中原子的量子理论(QTAIM)和局部振动模式理论等成键模型相一致,揭示了极性键中重叠密度向电负性更强的原子移动等观点。使用 OP/TOP 描述因子的锂-F 解离曲线显示了在锂-F 解离过程中对离子/中性反转的敏感性,凸显了它们在阐明复杂键现象方面的潜力,并为理解多构型化学键动力学提供了新途径。
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来源期刊
CiteScore
6.60
自引率
3.30%
发文量
247
审稿时长
1.7 months
期刊介绍: This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.
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