Further investigations into a Laplace MP2 method using range separated Coulomb potential and Orbital Selective Virtuals: Multipole correction, OSV extrapolation and critical assessment

0569771 - ÚFCH JH 2024 RIV US eng J - Článek v odborném periodiku
Demel, Ondřej - Lecours, M. J. - Nooijen, M.
Further investigations into a Laplace MP2 method using range separated Coulomb potential and Orbital Selective Virtuals: Multipole correction, OSV extrapolation and critical assessment.
Journal of Chemical Physics. Roč. 158, č. 11 (2023), č. článku 114120. ISSN 0021-9606. E-ISSN 1089-7690
Grant CEP: GA ČR(CZ) GA19-01897S
Institucionální podpora: RVO:61388955
Klíčová slova: Laplace MP2 method * Fourier transform * Coulomb potential
Obor OECD: Physical chemistry
Impakt faktor: 4.4, rok: 2022
Způsob publikování: Open access

We report further investigations to aid the development of a Laplace MP2 (second-order Møller Plesset) method with a range separated Coulomb potential partitioned into short- and long-range parts. The implementation of the method extensively uses sparse matrix algebra, density fitting techniques for the short-range part, and a Fourier transformation in spherical coordinates for the long-range part of the potential. Localized molecular orbitals are employed for the occupied space, whereas virtual space is described by orbital specific virtual orbitals (OSVs) associated with localized molecular orbitals. The Fourier transform is deficient for very large distances between localized occupied orbitals, and a multipole expansion for widely separated pairs is introduced for the direct MP2 contribution, which is applicable also to non-Coulombic potentials that do not satisfy the Laplace equation. For the exchange contribution, an efficient screening of contributing localized occupied pairs is employed, which is discussed more completely here. To mitigate errors due to the truncation of OSVs, a simple and efficient extrapolation procedure is used to obtain results close to MP2 for the full basis set of atomic orbitals Using a suitable set of default parameters, the accuracy of the approach is demonstrated. The current implementation of the approach is not very efficient, and the aim of this paper is to introduce and critically discuss ideas that can have more general applicability beyond MP2 calculations for large molecules.
Trvalý link: https://hdl.handle.net/11104/0341108