Density-Matrix Based Scheme of Basis Selection for Linear Combination of Fragment Molecular Orbitals

A dependable description of the frontier orbitals around the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) is essential for the theoretical elucidation of exciton and charge-transfer dynamics in molecular systems. In this study, an efficient scheme for...

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Bibliographic Details
Published in:Journal of the Physical Society of Japan 2021-06, Vol.90 (6), p.64301
Main Authors: Okiyama, Yoshio, Mochizuki, Yuji, Yamanaka, Masanori, Tanaka, Shigenori
Format: Article
Language:English
Subjects:
Charge transfer
Data compression
Density
Dimers
Excitons
Glycine
Mathematical analysis
Molecular orbitals
Monomers
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Summary:A dependable description of the frontier orbitals around the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) is essential for the theoretical elucidation of exciton and charge-transfer dynamics in molecular systems. In this study, an efficient scheme for constructing molecular orbitals (MOs) of large molecular systems is proposed within the framework of the fragment molecular orbital (FMO) method. In contrast to the previously proposed energy-based methodology, called the linear combination of molecular orbitals of FMO (FMO-LCMO), the present scheme employs the density matrices of monomer and dimer MOs of fragments to select the monomer MOs as the basis set for constructing the Hamiltonian matrix of the total system. The accuracy and computational cost of the proposed scheme are assessed in comparison with those of the conventional energy-based methods for three model systems of DNA stacked base pairs, pseudo-glycine pentamer, and water clusters, thus demonstrating its efficiency in terms of data compression.
ISSN:0031-9015
1347-4073
DOI:10.7566/JPSJ.90.064301