期刊
JOURNAL OF COMPUTATIONAL CHEMISTRY
卷 39, 期 27, 页码 2283-2299出版社
WILEY
DOI: 10.1002/jcc.25548
关键词
atomic interaction line; bond path; FALDI; chemical bond; intramolecular interaction
资金
- National Research Foundation of South Africa [105855]
The total electron density (ED) along the (2)-eigenvector is decomposed into contributions which either facilitate or hinder the presence of an electron density bridge (DB, often called an atomic interaction line or a bond path). Our FALDI-based approach explains a DB presence as a result of a dominating rate of change of facilitating factors relative to the rate of change of hindering factors; a novel and universal criterion for a DB presence is, thus, proposed. Importantly, facilitating factors show, in absolute terms, a concentration of ED in the internuclear region as commonly observed for most chemical bonds, whereas hindering factors show a depletion of ED in the internuclear region. We test our approach on four intramolecular interactions, namely (i) an attractive classical H-bond, (ii) a repulsive OO interaction, (iii) an attractive ClCl interaction, and (iv) an attractive CHHC interaction. (Dis)appearance of a DB is (i) shown to be due to a small change in molecular environment and (ii) qualitatively and quantitatively linked with specific atoms and atom-pairs. The protocol described is equally applicable (a) to any internuclear region, (b) regardless of what kind of interaction (attractive/repulsive) atoms are involved in, (c) at any level of theory used to compute the molecular structure and corresponding wavefunction, and (d) equilibrium or nonequilibrium structures. Finally, we argue for a paradigm shift in the description of chemical interactions, from the ED perspective, in favor of a multicenter rather than diatomic approach in interpreting ED distributions in internuclear regions. (c) 2018 Wiley Periodicals, Inc.
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