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Tetrel bonding interaction: an analysis with the block-localized wavefunction (BLW) approach.

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Tetrel bonding interactions are dominated by electrostatic forces, according to block-localized wave function (BLW) energy decomposition. Charge transfer interactions also contribute positively to tetrel bond stabilization.

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Area of Science:

  • Computational chemistry
  • Quantum chemistry
  • Non-covalent interactions

Background:

  • Tetrel bonding is a significant non-covalent interaction involving tetrel elements (Group 14).
  • Understanding the energetic contributions to tetrel bonding is crucial for predicting molecular interactions and reactivity.

Purpose of the Study:

  • To investigate the energetic components of tetrel bonding using the block-localized wave function (BLW) method.
  • To analyze the role of electrostatic potential and charge transfer in stabilizing tetrel bonded complexes.
  • To provide a simplified electrostatic model for tetrel bonding.

Main Methods:

  • Utilized the block-localized wave function (BLW) method to obtain self-consistent wave functions for electron-localized states.
  • Performed energy decomposition analysis (BLW-ED) to quantify interaction energies.
  • Analyzed electrostatic potential (ESP) variations along the binding direction for monomers.
  • Employed empirical point charges to model σ-holes for electrostatic interaction analysis.

Main Results:

  • Frozen energy, primarily Pauli repulsion and electrostatics, dominates in 31 of 51 studied tetrel bonding complexes.
  • Stronger electrostatic potential (ESP) in Lewis bases correlates with higher stabilizing frozen and polarization energies.
  • Charge transfer interactions positively contribute to tetrel bond strength, as evidenced by BLW-ED and bond weakening when disabled.
  • A simplified electrostatic model using point charges successfully explains attractive interactions in tetrel bonding.

Conclusions:

  • Electrostatic interactions are the primary drivers of stabilization in many tetrel bonding systems.
  • Charge transfer, while secondary, plays a confirmed positive role in tetrel bond formation.
  • The study offers a simplified electrostatic perspective on tetrel bonding, highlighting the importance of σ-holes.