Premium
Symmetry breaking and its influence on the correlation energy for CF 4 + and CF 3 2+ ions
Author(s) -
Garcia de la vega J. M.,
San fabian E.
Publication year - 1994
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.560520420
Subject(s) - electronic correlation , symmetry (geometry) , ion , symmetry breaking , chemistry , open shell , wave function , explicit symmetry breaking , physics , atomic physics , hartree–fock method , molecular physics , quantum mechanics , molecule , spontaneous symmetry breaking , geometry , mathematics
We have studied symmetry breaking in three open‐shell systems: CF 4 +( D 2 d and C 2 v ) and CF 3 2+( D 3 h ) molecular ions. These different Hartree–Fock solutions are employed as starting points to calculate the correlation energy of these ions with perturbative, configuration interaction, and density functional methods. When symmetry‐broken or symmetry‐adapted wave functions are used, the correlation energy obtained with each method changes the order of stability of CF 4 +for a determined symmetry. Density functional methods produce higher correlation energies although they do not alter the order of stability of Hartree–Fock calculations. The behavior of correlation energy with different methods and the characteristics of the symmetry of wave functions are compared. A study of appearance energies for three different channels of the decomposition reaction of ionized carbon tetrafluoride are considered by using different methods with symmetry‐broken or symmetry‐adapted wave functions to calculate correlation energies. © 1994 John Wiley & Sons, Inc.