Benchmarking second order methods for the calculation of vertical electronic excitation energies: valence and Rydberg states in polycyclic aromatic hydrocarbons

Heidi H Falden; Kasper R Falster-Hansen; Keld L Bak; Sten Rettrup; Stephan P A Sauer

doi:10.1021/jp9037123

Benchmarking second order methods for the calculation of vertical electronic excitation energies: valence and Rydberg states in polycyclic aromatic hydrocarbons

J Phys Chem A. 2009 Oct 29;113(43):11995-2012. doi: 10.1021/jp9037123.

Authors

Heidi H Falden¹, Kasper R Falster-Hansen, Keld L Bak, Sten Rettrup, Stephan P A Sauer

Affiliation

¹ Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100, Copenhagen Ø, Denmark.

PMID: 19780572
DOI: 10.1021/jp9037123

Abstract

The performance of the six second order linear response methods RPA(D), SOPPA, SOPPA(CCSD), CIS(D), CC2, and CCSD, which include either noniterative or iterative doubles contributions, has been studied in calculations of vertical excitation energies. The benchmark set consisted of 39 valence and 76 Rydberg states of benzene and five polycyclic aromatic hydrocarbons. As reference values we have used the results of the corresponding calculations with the third order method CCSDR(3), which includes noniterative triples contributions. In addition we have also carried out equivalent calculations at the level of the random phase approximation as well as with the configuration interaction singles and multireference configuration interaction singles and doubles methods.