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Molecular tight‐binding method. I. Many‐electron method for hole bands of molecular crystals
Author(s) -
Stolarczyk Leszek Z.
Publication year - 1982
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560210603
Subject(s) - exciton , tight binding , crystal (programming language) , intramolecular force , electron , electronic correlation , electron hole , relaxation (psychology) , molecular physics , ion , electronic band structure , chemistry , atomic physics , electronic structure , physics , condensed matter physics , quantum mechanics , psychology , social psychology , computer science , programming language
A method for calculating ab initio electronic excitation energies of molecular crystals, based on a many‐electron tight‐binding approximation, is described. The method follows Frenkel's model for excitons and allows a many‐electron treatment of the band‐structure problem of molecular crystals. The case of hole bands is studied in detail and various versions of the method are considered. A computational scheme is proposed, in which approximate correlation corrections to the HFR matrix equations of the one‐electron LCMO method are calculated. The main effects contributing to these corrections are the effect of relaxation of a molecular ion, the effect of intramolecular electronic‐correlation change, and the effect of polarization of the remaining molecules in a crystal. The method developed in the present paper is applied to calculation of the hole bands of the HCP helium crystal.