Ab initio anharmonic calculations of vibrational frequencies of benzene by means of efficient construction of potential energy functions

An efficient technique constructing anharmonic potential energy functions was applied to ab initio vibrational analysis of benzene. Anharmonic potentials including the 6-order terms, much higher than the full quartic force field, were automatically generated by a second-order algorithm using the scaled hypersphere search method, and vibrational calculations were performed at the level of VQDPT[1+ 2]. In comparison with previously reported anharmonic calculations, the present approach gave an excellent ab initio result for in-plane modes including the b(2u) so called Kekule mode. Characteristic properties of various approaches were discussed in connection with the anharmonic effects and the strong vibronic effects. (C) 2011 Elsevier B.V. All rights reserved.