Time-dependent density functional theory calculations of molecular static and dynamic polarizabilities, cauchy coefficients and their anisotropies with atomic numerical basis functions

Abstract Static and dynamic polarizabilities of a range of small first row compounds have been calculated with time-dependent density functional theory in the local spin-density approximation using numerical atomic basis sets. The results are compared to earlier computational work, in particular the work of Van Caillie and Amos [C. Van Caillie, R.D. Amos, Chem. Phys. Lett. 291 (1998) 71], as well as experimental values. The results for static isotropic and anisotropic polarizabilities of H 2 O, N 2 , CO, NH 3 , and CH 4 are in good agreement with previous calculations. The results for the dynamic polarizabilities as expressed in the S (−4) Cauchy coefficients and their anisotropies for H 2 O, N 2 , CO 2 , NH 3 , CH 4 , C 2 H 2 , C 2 H 4 and C 2 H 6 are also in good agreement with previous results. We have also explored the scaling of our implementation of the time-dependent coupled-perturbed Kohn–Sham equations by evaluating the static and dynamic polarizabilities of bifurcated water chains ranging from 1–20 molecules in size.

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