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Gaussian-4 theory using reduced order perturbation theory.
MedLine Citation:
PMID:  17902891     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
Two modifications of Gaussian-4 (G4) theory [L. A. Curtiss et al., J. Chem. Phys. 126, 084108 (2007)] are presented in which second- and third-order perturbation theories are used in place of fourth-order perturbation theory. These two new methods are referred to as G4(MP2) and G4(MP3), respectively. Both methods have been assessed on the G3/05 test set of accurate experimental data. The average absolute deviation from experiment for the 454 energies in this test set is 1.04 kcalmol for G4(MP2) theory and 1.03 kcalmol for G4(MP3) theory compared to 0.83 kcalmol for G4 theory. G4(MP2) is slightly more accurate for enthalpies of formation than G4(MP3) (0.99 versus 1.04 kcalmol), while G4(MP3) is more accurate for ionization potentials and electron affinities. Overall, the G4(MP2) method provides an accurate and economical method for thermochemical predictions. It has an overall accuracy for the G3/05 test set that is much better than G3(MP2) theory (1.04 versus 1.39 kcalmol) and even better than G3 theory (1.04 versus 1.13 kcalmol). In addition, G4(MP2) does better for challenging hypervalent systems such as H(2)SO(4) and for nonhydrogen species than G3(MP2) theory.
Authors:
Larry A Curtiss; Paul C Redfern; Krishnan Raghavachari
Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  127     ISSN:  0021-9606     ISO Abbreviation:  J Chem Phys     Publication Date:  2007 Sep 
Date Detail:
Created Date:  2007-10-01     Completed Date:  2007-11-09     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  United States    
Other Details:
Languages:  eng     Pagination:  124105     Citation Subset:  -    
Affiliation:
Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
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