Accurate Ab initio potential energy surface and vibration-rotation energy levels of hydrogen peroxide

Authors:

• Paweł Małyszek,
• Jacek Koput

Abstract

The accurate ground-state potential energy surface of hydrogen peroxide, H₂O₂, has been determined from ab initio calculations using the coupled-cluster approach in conjunction with the correlation- consistent basis sets up to septuple-zeta quality. Results obtained with the conventional and explicitly correlated coupled-cluster methods were compared. The core-electron correlation, scalar relativistic, and higher-order valence-electron correlation effects were taken into account. The adiabatic effects were also discussed. The vibration-rotation energy levels of the H ₂O₂, D₂O₂, and HOOD isotopologues were predicted, and the experimental vibrational fundamental wavenumbers were reproduced to 1 cm^-1 ("spectroscopic") accuracy. © 2012 Wiley Periodicals, Inc.