Physics – Condensed Matter – Materials Science
Scientific paper
2009-07-08
J. Chem. Phys. 131, 154116 (2009)
Physics
Condensed Matter
Materials Science
13 pages, 3 figures, final version accepted for publication
Scientific paper
10.1063/1.3249966
We introduce a method for accurate quantum chemical calculations based on a simple variational wave function, defined by a single geminal that couples all the electrons into singlet pairs, combined with a real space correlation factor. The method uses a constrained variational optimization, based on an expansion of the geminal in terms of molecular orbitals. It is shown that the most relevant non-dynamical correlations are correctly reproduced once an appropriate number $n$ of molecular orbitals is considered. The value of $n$ is determined by requiring that, in the atomization limit, the atoms are described by Hartree-Fock Slater determinants with Jastrow correlations. The energetics, as well as other physical and chemical properties, are then given by an efficient variational approach based on standard quantum Monte Carlo techniques. We test this method on a set of homonuclear (Be2, B2, C2, N2, O2, and F2) and heteronuclear (LiF, and CN) dimers for which strong non-dynamical correlations and/or weak van der Waals interactions are present.
Azadi Sam
Casula Michele
Marchi Massimo
Sorella Sandro
No associations
LandOfFree
Resonating valence bond wave function with molecular orbitals: Application to first-row molecules does not yet have a rating. At this time, there are no reviews or comments for this scientific paper.
If you have personal experience with Resonating valence bond wave function with molecular orbitals: Application to first-row molecules, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Resonating valence bond wave function with molecular orbitals: Application to first-row molecules will most certainly appreciate the feedback.
Profile ID: LFWR-SCP-O-320090