Specific solute-solvent interactions: The ethene+...Ar complex

Gregory D. Scholes, Richard D. Harcourt, Ian R. Gould, David Phillips

Research output: Contribution to journalArticle

3 Scopus citations

Abstract

A molecule-based description of charge delocalization is introduced to describe interactions which depend upon intermolecular orbital overlap in order to investigate the origin of stabilization in specific solute-solvent complexes. Ionization potentials of aromatic "solute" molecules are shifted to lower energy in rare gas clusters, which has been attributed previously to charge-induced dipole interactions; however, the present work reveals that a charge "delocalization" mechanism may be operative in certain systems. This is due primarily to charge-transfer (CT) effects. A relationship between this interaction and the difference between solute and solvent ionization potentials is derived. The ethene+...Ar complex is examined as a specific case. We report the results of ab initio molecular orbital (MO), localized molecular orbital (LMO), and valence-bond (VB) studies of the C2H4+...Ar complex to provide a VB rationalization for the origin of the stability of the complex. The advantage of the VB treatment employed in the present work is that it allows a natural separation between polarization and CT terms, so it could be shown that the CT interaction provides a key contribution to the stabilization of the C2H4+...Ar complex. These results suggest that intermolecular charge-transfer resonances may to play a significant role in delocalizing charge among a charged ("solute") molecule and suitably proximate neutral ("solvent") molecules in a cluster.

Original languageEnglish (US)
Pages (from-to)678-684
Number of pages7
JournalJournal of Physical Chemistry A
Volume101
Issue number4
DOIs
StatePublished - Jan 23 1997
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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