English

A global potential energy surface for H$_3^+$

Chemical Physics 2018-12-17 v1

Abstract

A globally correct potential energy surface (PES) for the \hp\ molecular ion is presented. The Born-Oppenheimer (BO) \ai\ grid points of Pavanello et. al. [\textit{J. Chem. Phys.} {\bf 136}, 184303 (2012)] are refitted as BOPES75K, which reproduces the energies below dissociation with a root mean square deviation of 0.05~\cm; points between dissociation and 75\,000 \cm\ 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 \hp\ global potential to date, overcoming the limitations on previous high accuracy H3+_3^+ PESs near and above dissociation. PES75K+ can be used to provide predictions of bound rovibrational energy levels with an accuracy of approaching 0.1~\cm. 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_2 prototypical chemical reaction. An improved dissociation energy for H3+_3^+ is derived as D0=D_0\,=\,35\,076\,±2\pm\,2\,cm1^{-1}.

Keywords

Cite

@article{arxiv.1812.06035,
  title  = {A global potential energy surface for H$_3^+$},
  author = {I. I. Mizus and O. L. Polyansky and Laura K. McKemmish and J. Tennyson and A. Alijah and N. F. Zobov},
  journal= {arXiv preprint arXiv:1812.06035},
  year   = {2018}
}

Comments

20 pages, 4 figures, 6 tables

R2 v1 2026-06-23T06:42:50.644Z