Non-adiabatic mass correction to the rovibrational states of molecules. Numerical application for the H${}_2^{+}$ molecular ion

Abstract

General transformation expressions of the second-order non-adiabatic Hamiltonian of the atomic nuclei, including the kinetic-energy correction terms, are derived upon the change from laboratory-fixed Cartesian coordinates to general curvilinear coordinate systems commonly used in rovibrational computations. The kinetic-energy or so-called "mass-correction" tensor elements are computed with the stochastic variational method and floating explicitly correlated Gaussian functions for the H${}_2^{+}$ molecular ion in its ground electronic state. (Further numerical applications for the ${}^4$He${}_2^{+}$ molecular ion are presented in the forthcoming paper, Paper II.) The general, curvilinear non-adiabatic kinetic energy operator expressions are used in the examples and non-adiabatic rovibrational energies and corrections are determined by solving the rovibrational Schrödinger equation including the diagonal Born--Oppenheimer as well as the mass-tensor corrections.