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Long-range corrected double-hybrid density functionals
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On the difference between the transition properties calculated with linear response- and equation of motion-CCSD approaches

J. Chem. Phys. 131, 174104 (2009); doi:10.1063/1.3255990

Published 2 November 2009

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Marco Caricato,1,2 Gary W. Trucks,2 and Michael J. Frisch2
1Department of Chemistry, Yale University, 225 Prospect St., New Haven, Connecticut 06511, USA
2Gaussian, Inc., 340 Quinnipiac. St., Bldg. 40, Wallingford, Connecticut 06492, USA
In this work, we quantitatively investigate the difference between the linear response (LR) and the equation of motion (EOM) coupled cluster (CC) approaches in the calculation of transition properties, namely, dipole and oscillator strengths, for the most widely used truncated CC wave function, which includes single and double excitation operators. We compare systems of increasing size, where the size-extensivity may be important. Our results suggest that, for small molecules, the difference is small even with large basis sets. The difference increases with the size of the system, but it is numerically small until hundreds of electron pairs are correlated. Although these calculations may be possible in a few years, at present the EOM approach is more advantageous, albeit more approximate, because it is computationally less demanding. ©2009 American Institute of Physics
History: Received 30 August 2009; accepted 7 October 2009; published 2 November 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/174104/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.bw
    Coupled-cluster theory
  • 33.70.Ca
    Molecular oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors
  • YEAR: 2009

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (21)
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