Impact of local and density fitting approximations on harmonic vibrational frequencies.
Harmonic vibrational frequencies are computed using second-order Møller-Plesset perturbation theory (MP2) with and without local (LMP2) and density fitting (DF) approximations. Results for a test set of 17 small and medium size molecules (366 normal modes) are presented, and frequency scaling factors for LMP2 in combination with two different basis sets are determined. Comparison of the MP2 and LMP2 frequencies with experimental data reveals that the introduction of local approximations leads to a slightly better agreement with experiment. This is attributed to the reduction of basis set superposition errors in local calculations. Introduction of DF approximations within the LMP2 formalism leads to negligible deviations but significantly reduces the computational cost. These facts extend the applicability of the method to larger systems with large basis sets. As an example, the method is applied to a full DF-LMP2/cc-pVTZ frequency calculation for testosterone (49 atoms).
Hrenar
Tomica
T
Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
Rauhut
Guntram
G
Werner
Hans-Joachim
HJ