Bonding properties of chlorine oxides ClO x ( x=1–4) in the density functional theory

Abstract

The geometries, energies, heats of formation and bond dissociation energies of the chlorine oxides ClO x ( x=1–4) were computed at the restricted open shell BECKE3LYP/cc-pV5Z level; vibrational wavenumbers and intensities were calculated employing the cc-pVQZ basis set. The mean absolute deviation between the calculated and newest experimental enthalpies of formation was 5.3 kJ mol −1. A tetrahedral-like C 2v minimum geometry of the recently described ClO 4 radical was calculated, whereas the hitherto assumed C 3v structure was characterized as an energetically higher-lying second-order saddlepoint.