Document Type
Article
Subject Area(s)
Chemical Physics
Abstract
We introduce and investigate a chemical model based on perturbative corrections to the product of singlet-type strongly orthogonal geminals wave function. Two specific points are addressed (i) Overall chemical accuracy of such a model with perturbative corrections at a leading order; (ii) Quality of strong orthogonality approximation of geminals in diverse chemical systems. We use the Epstein–Nesbet form of perturbation theory and show that its known shortcomings disappear when it is used with the reference Hamiltonian based on strongly orthogonal geminals. Application of this model to various chemical systems reveals that strongly orthogonal geminals are well suited for chemical models, with dispersion interactions between the geminals being the dominant effect missing in the reference wave functions.
Publication Info
Published in The Journal of Chemical Physics, Volume 120, Issue 10385, 2004.
Rights
Copyright 2004 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.
The following article appeared in
Rassolov, V. A., Xu, F., & Garashchuk, S. (2004). Geminal model chemistry II. Perturbative corrections. The Journal of Chemical Physics, 120, 10385. http://dx.doi.org/10.1063/1.1738110
and may be found at
http://scitation.aip.org/content/aip/journal/jcp/120/22/10.1063/1.1738110