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Ab initio calculations including electron correlation for the minimum energy path of the ( 1 A 1 ) CH 2 +( 1 Σ g + )H 2 → ( 1 A 1 ) CH 4 insertion reaction
Author(s) -
Jeziorek Danuta,
Żurawski Bronisław
Publication year - 1979
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.560160210
Subject(s) - chemistry , ab initio , electronic correlation , atomic orbital , atomic physics , configuration interaction , ab initio quantum chemistry methods , electron pair , valence (chemistry) , electron , molecular physics , physics , molecule , quantum mechanics , excited state , organic chemistry
Ab initio calculations on the SCF level and with the inclusion of valence shell electron correlation in the IEPA–PNO (independent electron pair approximation with pair natural orbitals), the PNO–CI (pair‐natural‐orbital configuration interaction) and the CEPA–PNO (coupled electron pair approximation with pair natural orbitals) schemes with Gaussian lobe functions of “double zeta quality” have been performed for the minimum energy path of the insertion of singlet ( 1 A 1 ) methylene to the ( 1 Σ g + )H 2 molecule to yield methane. The energy was minimized on the SCF level to all geometrical parameters for various values of the “approximate” reaction coordinate. The energy along the reaction path decreases monotonically without a barrier and the curves representing the total energy of the system as a function of approximate reaction coordinates obtained at different levels of approximations have the same shape. From the physical point of view three phases of the reaction can be distinguished (chemically two steps) with different geometrical arrangements and different internal geometries of the partners.