Applicability of medium-size basis sets in calculation of electric dipole dynamic polarisabilities and first hyperpolarisabilities of non-interacting molecules

Abstract

Static and dynamic electric dipole polarisabilities and first hyperpolarisabilities of test molecules are evaluated within the CCSD response approach using medium-size basis sets: the large polarised LPol-n (n = ds, dl, fs, fl) sets, the aug-pc-n (n = 1, 2) basis sets of Jensen, and the SVPD and TZVPD basis sets of Rappoport and Furche. Results are compared to reference values obtained using the x-aug-cc-pVXZ (x= –, d, t; X = D, T, Q, 5) basis sets of Dunning. The aug-pc-2 basis set of Jensen proves to be an attractive choice in the case of polarisability calculations, and among the smaller sets, the LPol-ds and the TZVPD basis sets can be recommended. For the first hyperpolarisability calculations, we recommend in particular the use of the LPol-ds basis set. Other attractive choices here are the LPol-dl, the LPol-fs and the aug-pc-2 sets.

Keywords:

• electric dipole polarisability
• first electric dipole hyperpolarisability
• medium-size basis sets
• CCSD response approach
• isolated molecules
• CC3

Acknowledgements

This work is supported by the Foundation for Polish Science within the Homing Plus programme (Homing Plus/2010-1/2), co-financed from European Regional Development Fund within Innovative Economy Operational Programme.