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A comparative study on the bond features in CO, CS, and PbS.

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This study reveals how electrostatic and covalent interactions differ in CO, CS, and PbS molecules. It shows that dipole moments and electron affinity increase with electrostatic dominance, with CS being a promising ligand.

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Area of Science:

  • Chemical Bonding and Molecular Interactions
  • Quantum Chemistry
  • Spectroscopy

Background:

  • Covalent and noncovalent interactions are fundamental in condensed and gas phases.
  • The diatomic molecule CO is typically viewed as a triple-bond system with a dative bond.

Purpose of the Study:

  • To investigate and compare the bonding characteristics of CO, CS, and PbS anions.
  • To elucidate the interplay of electrostatic and dative covalent interactions in these molecules.
  • To explore the potential of CS as a ligand in coordination chemistry.

Main Methods:

  • Photoelectron velocity-map imaging spectroscopy of CS and PbS anions.
  • Comparative analysis of electrostatic potential (ESP) and bond features.
  • Molecular orbital (MO) analyses.
  • Electron localization function (ELF), natural resonance theory (NRT), and bond order analyses.

Main Results:

  • CO exhibits competing electrostatic and dative covalent interactions with a small dipole moment.
  • CS is dominated by dative covalent interactions, possessing a large dipole moment.
  • PbS is dominated by electrostatic interactions, showing a large dipole moment and surprising Pb 5d orbital participation in bonding.
  • Electron affinity increases with dipole moment: CO < CS < PbS.
  • CS is identified as a promising ligand for transition-metal coordination synthesis.

Conclusions:

  • The study provides a detailed comparative analysis of bonding in CO, CS, and PbS.
  • It highlights the varying roles of electrostatic and covalent forces in determining molecular properties.
  • CS emerges as a significant molecule for coordination chemistry applications.