Basis set effects on coupled cluster benchmarks of electronically excited states: CC3, CCSDR(3) and CC2

Abstract

Vertical electronic excitation energies and one-electron properties of 28 medium-sized molecules from a previously proposed benchmark set are revisited using the augmented correlation-consistent triple-zeta aug-cc-pVTZ basis set in CC2, CCSDR(3), and CC3 calculations. The results are compared to those obtained previously with the smaller TZVP basis set. For each of the three coupled cluster methods, a correlation coefficient greater than 0.994 is found between the vertical excitation energies computed with the two basis sets. The deviations of the CC2 and CCSDR(3) results from the CC3 reference values are very similar for both basis sets, thus confirming previous conclusions on the intrinsic accuracy of CC2 and CCSDR(3). This similarity justifies the use of CC2- or CCSDR(3)-based corrections to account for basis set incompleteness in CC3 studies of vertical excitation energies. For oscillator strengths and excited-state dipole moments, CC2 calculations with the aug-cc-pVTZ and TZVP basis sets give correlation coefficients of 0.966 and 0.833, respectively, implying that basis set convergence is slower for these one-electron properties.

Keywords:

• electronically excited states
• benchmarks
• coupled cluster methods
• CC2
• CCSDR(3)
• CC3

Acknowledgements

This work was supported by the Deutsche Forschungsgemeinschaft (SFB 663, project C4). M.R.S.J. gladly acknowledges support by the Deutscher Akademischer Austauschdienst (DAAD). S.P.A.S. acknowledges support from the Danish Center for Scientific Computing (DCSC) and from the Danish Natural Science Research Council/The Danish Councils for Independent Research. We thank Prof. Christoph Hättig for helpful discussions.