Ab initio molecular study of hydrogen peroxide.: Application of density functional methods

Abstract

A systematic study of the abilities of a broad family of density functional methods and basis sets has been carried out on hydrogen peroxide. Calculations have been performed using different basis sets from 3-21G to 6-311+G(3d, 2p). Various local and non-local exchange, exchange-correlation and hybrid functionals have been applied in order to study the structure, energetic and vibrational properties of hydrogen peroxide. Comparison with experimental data and also with results from ab initio methods (HF and correlated levels) shows a good performance of non-local density functional methods for the description of the hydrogen peroxide geometry, especially the torsion angle τ, when we use basis sets of sufficient quality (at the least basis sets with a polarization function on oxygen). Different density functionals have been used in order to study cis and trans rotational transition states, using 6-31G(2d,p) and 6-31+G(2d,p) basis sets. The calculated torsional barriers and zero-point vibrational energies (ZPEs) are in very good agreement with experimental values.