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Systematic errors in the total energy of molecular wave functions calculated within the PRDDO approximations
Author(s) -
Throckmorton Linda,
Marynick Dennis S.
Publication year - 1985
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540060619
Subject(s) - total energy , ab initio , wave function , systematic error , energy (signal processing) , ab initio quantum chemistry methods , chain (unit) , atomic physics , physics , molecule , mathematics , quantum mechanics , statistics , psychology , displacement (psychology) , psychotherapist
We compare calculated total energies for 150 open‐chain molecules using ab initio methodology and the PRDDO approximations. The bulk of the errors implicit in the PRDDO approximations are apparently of a one‐center nature, i.e., they are due to the number and type of atoms in the molecule, and not the details of the molecular geometry. Atomic correction factors are developed which reduce the errors in the calculated total energy of PRDDO wave functions by a factor of eight relative to the ab initio reference calculations. PRDDO calculations on ring and cage compounds are shown to have additional systematic errors in the total energy.