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Charge transfer and dispersion interaction stabilization of the D 2 h isomer of O 4
Author(s) -
Harcourt Richard D.,
Pyper Nicholas
Publication year - 1998
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1998)68:2<129::aid-qua5>3.0.co;2-x
Subject(s) - antibonding molecular orbital , chemistry , valence (chemistry) , monomer , charge (physics) , dimer , transfer (computing) , intermolecular force , superposition principle , basis set , molecular physics , valence bond theory , atomic physics , interaction energy , dispersion (optics) , computational chemistry , chemical physics , molecular orbital , molecule , atomic orbital , physics , density functional theory , quantum mechanics , organic chemistry , polymer , parallel computing , computer science , electron
The results of some minimal basis set valence bond calculations, with an antibonding midbond molecular orbital (π m *) included, are reported for the D 2 h isomer of O 4 . The in‐plane π m *←π* excitations describe the charge transfer from each monomer, while the π*←π excitations on each monomer partially describe the intermolecular dispersive attractions. It is found that the charge‐transfer interactions by themselves are insufficient to stabilize the S =0 spin D 2 h dimer of O 4 relative to two O 2 monomers when a correction is included for basis set superposition error. The inclusion of both the charge transfer and dispersion terms yields an estimate of 14 cm −1 for the binding energy ( D e ) at an equilibrium separation ( R e ) of 3.29 Å. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 129–134, 1998