A b i n i t i o calculation of infrared intensities for hydrogen peroxide

Abstract

Infrared intensities are predicted for the fundamental vibrations of H2O2 using atomic polar tensors obtained from a b i n i t i o quantum mechanical calculations employing a 4‐31G basis set. The theoretical atomic polar tensors for H2O2 are compared to theoretical atomic polar tensors reported for H2O and for CH3OH, and the absolute intensities calculated quantum mechanically for H2O2 are compared to the previously reported intensities for H2O2 obtained by transferring a hydrogen atomic polar tensor to H2O2 from H2O and from CH3OH. These comparisons enable estimates to be made for the infrared intensities of H2O2 as follows: A 1 = 14.5 km mol−1, A 2 = 0.91 km mol−1, A 3 = 0.058 km mol−1, A 4 = 123 km mol−1, A 5 = 46.2 km mol−1, and A 6 = 101 km mol−1. Charge, charge flux, and overlap contributions to the dipole moment derivatives are computed for H2O2 and compared with those reported for H2O and CH3OH.