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Real space bonding descriptors offer an orbital-invariant way to understand chemical bonding. This study links these descriptors to Valence Bond theory concepts like ionic/covalent character and resonance.

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Area of Science:

  • Quantum Chemistry
  • Theoretical Chemistry
  • Chemical Bonding Theory

Background:

  • Valence Bond (VB) theory provides essential chemical insight through concepts like ionic/covalent character and resonance.
  • Traditional VB theory can present challenges in interpretation due to non-orthogonal basis sets.
  • Real space bonding descriptors offer an alternative, theoretically independent approach to analyzing chemical bonds.

Purpose of the Study:

  • To demonstrate the utility of real space bonding descriptors in interpreting Valence Bond theory concepts.
  • To establish a direct link between real space delocalization indices and ionic/covalent character.
  • To develop a real space ionic character index analogous to its VB counterpart.

Main Methods:

  • Utilized electron number distribution functions to analyze electron population fluctuations.
  • Employed real space delocalization indices to quantify covalent and ionic contributions.
  • Defined and tested a novel real space ionic character index using model systems.

Main Results:

  • Established that covalency, interpreted as electron delocalization, arises from electron population fluctuations in real space.
  • Mapped these real space delocalization phenomena to covalent-ionic resonance within the Valence Bond framework.
  • Successfully defined a simple real space ionic character index that reflects VB theory principles.

Conclusions:

  • Real space bonding descriptors provide a powerful, framework-independent method for understanding VB theory concepts.
  • The study bridges interpretations between molecular orbital, real space, and Valence Bond theories.
  • This work facilitates a more unified understanding of chemical bonding across different theoretical approaches.