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Updated: May 22, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Application of explicitly localized molecular orbitals to electronic structure calculations
Piotr de Silva1, Marcin Makowski, Jacek Korchowiec
1Department of Theoretical Chemistry Faculty of Chemistry, Jagiellonian University R. Ingardena 3, Kraków, Poland. desilva@chemia.uj.edu.pl
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.
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