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Calculation of molecular geometries and energies by a local density functional approach
Author(s) -
Seminario Jorge M.,
Concha Monica C.,
Politzer Peter
Publication year - 1991
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.560400825
Subject(s) - gaussian , density functional theory , ab initio , dissociation (chemistry) , atomic physics , chemistry , polarization (electrochemistry) , bond dissociation energy , computational physics , molecular physics , computational chemistry , physics , organic chemistry
Abstract We have used density functional theory in the local density approximation, as implemented in the DMol–double numerical plus polarization (DMol/ DNP ) procedure, to calculate optimized geometries for a group of molecules containing only first‐row atoms. The results are in generally satisfactory agreement with experimentally determined structures. The DMol/ DNP atomic and molecular energies are rather poor, when compared to high‐level ab initio GAUSSIAN 1 values (which are taken as the standard), but the errors do show excellent linear correlations with the total energies. These relationships allow the DMol/ DNP results to be corrected to a high degree of accuracy, so that they can then be used to obtain atomization and dissociation energies that compare well with measured values. It is shown that the errors in the DMol/ DNP energies tend to increase as the number of electrons becomes larger and the number of nuclei smaller.