A global potential energy surface for H3+
Abstract
A globally correct potential energy surface (PES) for the \ molecular ion is presented. The Born-Oppenheimer (BO) \ grid points of Pavanello et. al. [J. Chem. Phys. 136, 184303 (2012)] are refitted as BOPES75K, which reproduces the energies below dissociation with a root mean square deviation of 0.05~; points between dissociation and 75\,000 \ are reproduced with the average accuracy of a few wavenumbers. The new PES75K+ potential combines BOPES75K with adiabatic, relativistic and quantum electrodynamics (QED) surfaces to provide the most accurate representation of the \ global potential to date, overcoming the limitations on previous high accuracy H3+ PESs near and above dissociation. PES75K+ can be used to provide predictions of bound rovibrational energy levels with an accuracy of approaching 0.1~. Calculation of rovibrational energy levels within PES75K+ suggests that the non-adiabatic correction remains a limiting factor. The PES is also constructed to give the correct asymptotic limit making it suitable for use in studies of the H+\,+\,H2 prototypical chemical reaction. An improved dissociation energy for H3+ is derived as D0\,=\,35\,076\,\,2\,cm-1.
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