Structure and dynamics of HD$^+$ in the vicinity of the H$^+$ + D and D$^+$ + H dissociation thresholds: Feshbach resonances and the role of g/u-symmetry breaking

TL;DR

This study investigates the structure and dynamics of HD$^+$ near dissociation thresholds, revealing Feshbach resonances and the impact of g/u-symmetry breaking due to nuclear-mass asymmetry through detailed spectroscopic analysis.

Contribution

First observation of shape and Feshbach resonances of HD$^+$ above dissociation limits, highlighting the effects of g/u-symmetry breaking on molecular states.

Findings

Identification of weakly bound levels of HD$^+$

Observation of Feshbach and shape resonances

Demonstration of g/u-symmetry breaking effects

Abstract

We report on the measurement and analysis of photoionisation, mass-analysed-threshold-ionisation and pulsed-field-ionisation zero-kinetic-energy photoelectron spectra of HD in the vicinity of the dissociative-ionisation thresholds H$^+$ + D(1s) + e$^-$ and H(1s) + D$^+$ + e$^-$. The spectra were recorded via the $v=11$-13 vibrational levels of the $\bar{\rm H}$ and $\bar{\rm B}$ outer wells of the H$\bar{\rm H}$~$^1\Sigma_g^+$ and B$^{\prime\prime}\bar{\rm B}$~$^1\Sigma_u^+$ states and provide information on the weakly bound levels of the X$^+$ $^2\Sigma_g^+$ ground state of HD$^+$ with vibrational quantum numbers $v^+=16$-21 and rotational angular-momentum quantum numbers $N^+=0$-10. The spectra also reveal for the first time shape and Feshbach resonances of HD$^+$ located energetically above the H$^+$ + D(1s) dissociation limit. The structure and dissociation dynamics of the $\bar{\rm H}$ and $\bar{\rm B}$ states of HD and of the X$^+$ $^2\Sigma_g^+$ and A$^+$ $^2\Sigma_u^+$ states of HD$^+$ near the dissociation thresholds are strongly influenced by the g/u-symmetry breaking caused by the nuclear-mass asymmetry.