When Is a Bond Broken? The Polarizability Perspective.

Journal Article · 10 October 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202312078 · OSTI ID:2281432

Hait, Diptarka  ^[1]; Head‐Gordon, Martin  ^[2]

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1. Kenneth S. Pitzer Center for Theoretical Chemistry Department of Chemistry University of California, Berkeley Berkeley CA 94720 USA, Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA, Department of Chemistry and PULSE Institute Stanford University Stanford CA 94305 USA
2. Kenneth S. Pitzer Center for Theoretical Chemistry Department of Chemistry University of California, Berkeley Berkeley CA 94720 USA, Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Abstract The question of when a chemical bond can be said to be broken is of fundamental chemical interest but has not been widely studied. Herein we propose that the maxima of static polarizability along bond dissociation coordinates naturally define cutoff points for bond rupture, as they represent the onset of localization of shared electron density into constituent fragments. Examples of computed polarizability maxima over the course of bond cleavage in main‐group and transition metal compounds are provided, across covalent, dative and charge‐shift bonds. The behavior along reaction paths is also considered. Overall, the static polarizability is found to be a sensitive reporter of electronic structure reorganization associated with bond stretching, and thus can serve as a metric for describing bond cleavage (or diagnose the absence of a chemical bond).

• Sponsoring Organization: USDOE
• Grant/Contract Number: NONE; SC0021266; AC02-05CH11231
• OSTI ID: 2281432
• Journal Information: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 46 Vol. 135; ISSN 0044-8249
• Publisher: Wiley Blackwell (John Wiley & Sons)Copyright Statement
• Country of Publication: Germany
• Language: English