Variational calculation of highly excited rovibrational energy levels of H2O2

TL;DR

This paper presents highly accurate variational calculations of H2O2's rovibrational energy levels using advanced computational methods and a refined potential energy surface, achieving near-experimental accuracy for high rotational states.

Contribution

It introduces a combined variational approach with two different kinetic energy operators and refines the potential energy surface to accurately compute high-J rovibrational levels of H2O2.

Findings

Achieved a standard deviation of 0.002 cm⁻¹ for levels up to J=10.

Extended accurate energy level calculations up to J=35.

Demonstrated the effectiveness of combining different variational methods.

Abstract

Results are presented for highly accurate ab initio variational calculation of the rotation - vibration energy levels of H2O2 in its electronic ground state. These results use a recently computed potential energy surface and the variational nuclear-motion programmes WARV4, which uses an exact kinetic energy (EKE) operator, and TROVE, which uses a numerical expansion for the kinetic energy. The TROVE calculations are performed for levels with high values of rotational excitation, $J$ up to 35. The purely \ai\ calculations of the rovibrational energy levels reproduce the observed levels with a standard deviation of about 1 \cm, similar to that of the $J = 0$ calculation as the discrepancy between theory and experiment for rotational energies within a given vibrational state is substantially determined by the error in the vibrational band origin. Minor adjustments are made to the ab initio equilibrium geometry and to the height of the torsional barrier. Using these and correcting the band origins using the error in $J = 0$ states lowers the standard deviation of the observed $-$ calculated energies to only 0.002 \cm\ for levels up to $J = 10$ and 0.02 \cm\ for all experimentally know energy levels, which extend up to $J = 35$.