Fragment-Based Excited-State Calculations Using the GW Approximation and the Bethe-Salpeter Equation

被引:16
|
作者
Fujita, Takatoshi [1 ]
Noguchi, Yoshifumi [2 ]
机构
[1] Natl Inst Quantum Sci & Technol, Inst Quantum Life Sci, Tokai, Ibaraki 3191106, Japan
[2] Shizuoka Univ, Dept Appl Chem & Biochem Engn, Grad Sch Engn, Hamamatsu, Shizuoka 4328561, Japan
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2021年 / 125卷 / 49期
基金
日本学术振兴会;
关键词
MOLECULAR-ORBITAL METHOD; CONFIGURATION-INTERACTION SINGLES; COMPUTATIONAL METHOD; EXCITATION-ENERGY; IMPLEMENTATION; COMPLEXES; FORMALISM; CRYSTALS; DYNAMICS; FRENKEL;
D O I
10.1021/acs.jpca.1c07337
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Herein, we present a fragment-based approach for calculating the charged and neutral excited states in molecular systems, based on the many-body Green's function method within the GW approximation and the Bethe-Salpeter equation (BSE). The implementation relies on the many-body expansion of the total irreducible polarizability on the basis of fragment molecular orbitals. The GW quasi-particle energies in complex molecular environments are obtained by the GW calculation for the target fragment plus induced polarization contributions of the surrounding fragments at the static Coulomb-hole plus screened exchange level. In addition, we develop a large-scale GW/BSE method for calculating the delocalized excited states of molecular aggregates, based on the fragment molecular orbital method and the exciton model. The accuracy of fragment-based GW and GW/BSE methods was evaluated on molecular clusters and molecular crystals. We found that the accuracy of the total irreducible polarizability can be improved systematically by including two-body correction terms, and the fragment-based calculations can reasonably reproduce the results of the corresponding unfragmented calculations with a relative error of less than 100 meV. The proposed approach enables efficient excited-state calculations for large molecular systems with reasonable accuracy.
引用
收藏
页码:10580 / 10592
页数:13
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