Application of Explicitly Localized Molecular Orbitals to Electronic Structure Calculations

Authors

  • Piotr de Silva SCS-Metrohm Foundation Award winner for best oral presentation, Department of Theoretical Chemistry Faculty of Chemistry, Jagiellonian University R. Ingardena 3, 30-060 Kraków, Poland; Département de Chimie Physique Université de Genève 30, quai Ernest-Ansermet CH-1211 Genève 4, Switzerland desilva@chemia.uj.edu.pl
  • Marcin Makowski Department of Theoretical Chemistry Faculty of Chemistry, Jagiellonian University R. Ingardena 3, 30-060 Kraków, Poland. makowskm@chemia.uj.edu.pl
  • Jacek Korchowiec Department of Theoretical Chemistry Faculty of Chemistry, Jagiellonian University R. Ingardena 3, 30-060 Kraków, Poland. korchow@chemia.uj.edu.pl

DOI:

https://doi.org/10.2533/chimia.2012.178

Keywords:

Correlation energy, Local møller-plesset second-order perturbation theory (local mp2), Molecular orbital localization schemes, Regional localized molecular orbitals (rlmo)

Abstract

We have recently generalized the method for localizing orbitals on a set of predefined molecular fragments [Phys. Chem. Chem. Phys. 2012, 14, 546]. The regional localized molecular orbitals (RLMO) are well suited for exploiting the locality of electronic correlation at post-Hartree-Fock level of theory. In this paper, the adequacy of RLMO representation is tested in the second-order local Møller-Plesset (LMP2) perturbation theory. Two model systems, namely, n-pentadecane and trans-retinal, are considered. Adequacy of RLMO/LMP2 method is discussed in conjunction with 'exact' MP2 and Pipek-Mezey LMP2 calculations. It is demonstrated that RLMO/MP2 method reduces correlation space and reproduces more than 99% of the correlation energy.

Downloads

Published

2012-04-25

How to Cite