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Nondynamical correlation energy in model molecular systems
Author(s) -
Chojnacki Henryk
Publication year - 2008
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/qua.21749
Subject(s) - wave function , multireference configuration interaction , dissociation (chemistry) , basis set , deprotonation , chemistry , potential energy , electronic correlation , bond dissociation energy , computational chemistry , quantum , limit (mathematics) , physics , atomic physics , statistical physics , quantum mechanics , molecule , density functional theory , mathematics , ion , mathematical analysis
The hypersurfaces for the deprotonation processes have been studied at the nonempirical level for H 3 O + , NH + 4 , PH + 4 , and H 3 S + cations within their correlation consistent basis set. The potential energy curves were calculated and nondynamical correlation energies analyzed. We have found that the restricted Hartree‐Fock wavefunction leads to the improper dissociation limit and, in the three latest cases requires multireference description. We conclude that these systems may be treated as a good models for interpretation of the proton transfer mechanism as well as for testing one‐determinantal or multireference cases. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008