Chemical Bond Overlap Descriptors From Multiconfiguration Wavefunctions.

Autor: Santos-Jr CV; Department of Chemistry, Federal University of Paraiba, João Pessoa, Brazil., Kraka E; Department of Chemistry, Computational and Theoretical Chemistry Group (CATCO), Southern Methodist University, Dallas, Texas, USA., Moura RT Jr; Department of Chemistry, Computational and Theoretical Chemistry Group (CATCO), Southern Methodist University, Dallas, Texas, USA.; Department of Chemistry and Physics, Center of Agrarian Sciences, Federal University of Paraiba, Areia, Brazil.
Jazyk: angličtina
Zdroj: Journal of computational chemistry [J Comput Chem] 2025 Jan 05; Vol. 46 (1), pp. e27534.
DOI: 10.1002/jcc.27534
Abstrakt: 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, H 2 B, H 3 C, H 2 N, 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.
(© 2024 The Author(s). Journal of Computational Chemistry published by Wiley Periodicals LLC.)
Databáze: MEDLINE
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