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Lorenz, Marco ; Usvyat, Denis ; Schütz, Martin

Local ab initio methods for calculating optical band gaps in periodic systems. I. Periodic density fitted local configuration interaction singles method for polymers

Lorenz, Marco, Usvyat, Denis and Schütz, Martin (2011) Local ab initio methods for calculating optical band gaps in periodic systems. I. Periodic density fitted local configuration interaction singles method for polymers. The Journal of Chemical Physics 134 (9), 094101.

Date of publication of this fulltext: 07 Sep 2011 08:25
Article
DOI to cite this document: 10.5283/epub.22026


Abstract

We present a density fitted local configuration interaction singles (CIS) method for calculating optical band gaps in 1D-periodic systems. The method is based on the Davidson diagonalization procedure, carried out in the reciprocal space. The one-electron part of the matrix–vector products is also evaluated in the reciprocal space, where the diagonality of the Fock matrix can be exploited. The ...

We present a density fitted local configuration interaction singles (CIS) method for calculating optical band gaps in 1D-periodic systems. The method is based on the Davidson diagonalization procedure, carried out in the reciprocal space. The one-electron part of the matrix–vector products is also evaluated in the reciprocal space, where the diagonality of the Fock matrix can be exploited. The contraction of the CIS vectors with the two electron integrals is performed in the direct space in the basis of localized occupied (Wannier) and virtual (projected atomic) orbitals. The direct space approach allows to utilize the sparsity of the integrals due to the local representation and locality of the exciton. The density fitting approximation employed for the two electron integrals reduces the nominal scaling with unit cell size to O(N4). Test calculations on a series of prototypical systems demonstrate that the method in its present stage can be used to calculate the excitonic band gaps of polymers with up to a few dozens of atoms in the cell. The computational cost depends on the locality of the exciton, but even relatively delocalized excitons occurring in the polybiphenyl in the parallel orientation, can be routinely treated with this method.



Involved Institutions


Details

Item typeArticle
Journal or Publication TitleThe Journal of Chemical Physics
Publisher:American Institute of Physics (AIP)
Volume:134
Number of Issue or Book Chapter:9
Page Range:094101
Date2011
InstitutionsChemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Research Group Theoretical Chemistry > Prof. Dr. Martin Schütz
Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Research Group Theoretical Chemistry > PD Dr. Denis Usvyat
Identification Number
ValueType
10.1063/1.3554209DOI
Classification
NotationType
71.20.RvPACS
71.15.ApPACS
71.35.-yPACS
78.20.CiPACS
Keywordsab initio calculations; energy gap; excitons; HF calculations; optical constants; orbital calculations; periodic structures; polymers; tight-binding calculations
Dewey Decimal Classification500 Science > 530 Physics
500 Science > 540 Chemistry & allied sciences
StatusPublished
RefereedYes, this version has been refereed
Created at the University of RegensburgYes
URN of the UB Regensburgurn:nbn:de:bvb:355-epub-220268
Item ID22026

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