2004/09/24 by M. Casula, C. Attaccalite, S. Sorella · 1 citation
Physics and Astronomy · #cond-mat.other
paper · pdf · doi:10.1063/1.1794632
published as J. Chem. Phys. 121, 7110 (2004) · 20 pages, 5 figures, to be published in the Journal of Chemical Physics
arxiv created 2004/09/24 · arxiv updated 2009/12/01
We show that a simple correlated wave function, obtained by applying a Jastrow correlation term to an Antisymmetrized Geminal Power (AGP), based upon singlet pairs between electrons, is particularly suited for describing the electronic structure of molecules, yielding a large amount of the correlation energy. The remarkable feature of this approach is that, in principle, several Resonating Valence Bonds (RVB) can be dealt simultaneously with a single determinant, at a computational cost growing with the number of electrons similarly to more conventional methods, such as Hartree-Fock (HF) or Density Functional Theory (DFT). Moreover we describe an extension of the Stochastic Reconfiguration (SR) method, that was recently introduced for the energy minimization of simple atomic wave functions. Within this extension the atomic positions can be considered as further variational parameters, that can be optimized together with the remaining ones. The method is applied to several molecules from Li2 to benzene by obtaining total energies, bond lengths and binding energies comparable with much more demanding multi configuration schemes.