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When Is a Bond Broken? The Polarizability Perspective.

Diptarka Hait1,2,3, Martin Head-Gordon1,2

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Researchers propose using static polarizability maxima to define when chemical bonds break. This method identifies the point where electron density localizes into separate molecular fragments, offering a new metric for bond cleavage.

Keywords:
bond dissociationchemical bondingelectron localizationreaction pathsstatic polarizability

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Area of Science:

  • Chemical Physics
  • Quantum Chemistry
  • Computational Chemistry

Background:

  • Defining the precise moment of chemical bond rupture is a fundamental challenge in chemistry.
  • Existing methods for bond cleavage analysis are limited.
  • Understanding bond dissociation is crucial for reaction mechanisms and molecular stability.

Purpose of the Study:

  • To establish a reliable metric for determining chemical bond rupture.
  • To investigate the role of static polarizability in bond dissociation.
  • To provide a new perspective on chemical bond analysis.

Main Methods:

  • Computational calculation of static polarizability along bond dissociation coordinates.
  • Analysis of polarizability maxima as indicators of electron density localization.
  • Examination of various chemical bond types (covalent, dative, charge-shift) in main-group and transition metal compounds.

Main Results:

  • Static polarizability maxima were identified as natural cutoff points for bond rupture.
  • These maxima correspond to the onset of shared electron density localization into fragments.
  • The study provides computed examples across diverse chemical bonds and reaction paths.
  • Static polarizability effectively reports electronic structure changes during bond stretching.

Conclusions:

  • Static polarizability serves as a sensitive and effective metric for describing bond cleavage.
  • This approach can diagnose the absence of a chemical bond.
  • The findings offer a novel method for analyzing chemical bond dynamics and stability.