Radiative lifetime of the $a\ ^3Σ^+$ state of HeH$^+$ from ab initio calculations

Abstract

The first metastable triplet state of HeH$^+$ was found to be present in ion beam experiments, with its lifetime estimated to be between hundreds of milliseconds and thousand of seconds. In this work, we use {\it ab initio} methods to evaluate the radiative lifetimes of the six vibrational levels of the $a\ ^3Σ^+$ of HeH$^+$. The transition $a\ ^3Σ^+ \rightarrow X \ ^1Σ^+$ is spin-forbidden, but acquires intensity through spin-orbit interaction with the singlet and triplet $Π$ states. Large scale CASSCF/MRCI calculations using an adapted basis set were performed to determine the potential energy curves of the relevant states of HeH$^+$ as well as the matrix elements of the dipole and spin-orbit operators. The wave functions and energies of the vibrational levels of the $a\ ^3Σ^+$ and $X \ ^1Σ^+$ states are obtained using a B-spline method and compared to previous works. We find that radiative lifetime of the vibrational levels increases strongly with $v$, the lifetime of the $v=0$ state being of 150 s. We also analyze the contributions from discrete and continuum parts of the spectrum. With such a long lifetime, the $a\ ^3Σ^+$ state could have astrophysical implications.