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

摘要

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_2O, 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_2O, N_2, CO_2, NH_3, CH_4, C_2H_2, C_2H_4 and C_2H_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.