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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 und 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.

Veröffentlichungsdatum dieses Volltextes: 07 Sep 2011 08:25
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.22026


Zusammenfassung

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.



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftThe Journal of Chemical Physics
Verlag:American Institute of Physics (AIP)
Band:134
Nummer des Zeitschriftenheftes oder des Kapitels:9
Seitenbereich:094101
Datum2011
InstitutionenChemie und Pharmazie > Institut für Physikalische und Theoretische Chemie > Arbeitskreis Theoretische Chemie (Theoretical Chemistry) > Prof. Dr. Martin Schütz
Chemie und Pharmazie > Institut für Physikalische und Theoretische Chemie > Arbeitskreis Theoretische Chemie (Theoretical Chemistry) > PD Dr. Denis Usvyat
Identifikationsnummer
WertTyp
10.1063/1.3554209DOI
Klassifikation
NotationArt
71.20.RvPACS
71.15.ApPACS
71.35.-yPACS
78.20.CiPACS
Stichwörter / Keywordsab initio calculations; energy gap; excitons; HF calculations; optical constants; orbital calculations; periodic structures; polymers; tight-binding calculations
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 530 Physik
500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenJa
URN der UB Regensburgurn:nbn:de:bvb:355-epub-220268
Dokumenten-ID22026

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