Systematic study of vibrational frequencies calculated with the self-consistent charge density functional tight-binding method.

Abstract

We present a detailed study of harmonic vibrational frequencies obtained with the self-consistent charge density functional tight-binding (SCC-DFTB) method. Our testing set comprises 66 molecules and 1304 distinct vibrational modes. Harmonic vibrational frequencies are computed using an efficient analytical algorithm developed and coded by the authors. The obtained results are compared to experiment and to other theoretical findings. Scaling factor for the SCC-DFTB method, determined by minimization of mean absolute deviation of scaled frequencies, is found to be 0.9933. The accuracy of the scaled SCC-DFTB frequencies is noticeably better than for other semiempirical methods (including standard DFTB method) and approximately twice worse than for other well established scaled ab initio quantum chemistry methods (e.g., HF, BLYP, B3LYP). Mean absolute deviation for the scaled SCC-DFTB frequencies is 56 cm(-1), while standard deviation is 82 cm(-1), and maximal absolute deviation is as large as 529 cm(-1). Using SCC-DFTB allows for substantial time savings; computational time is reduced from hours to seconds when compared to standard ab initio techniques.