Prediction of a Feshbach Resonance in the Below-the-Barrier Reactive Scattering of Vibrationally Excited HD with H

TL;DR

This study predicts a Feshbach resonance in low-energy vibrationally excited HD reacting with H, revealing new quantum effects in chemical reaction dynamics below the reaction barrier.

Contribution

First observation and detailed analysis of a Feshbach resonance in vibrationally excited HD + H reactive scattering at low energies.

Findings

Identification of a Feshbach resonance below the reaction barrier.

Resonance linked to coupling with the $v=1, j=1$ vibrational level.

Resonance dominated by a single partial wave.

Abstract

Quantum reactive scattering calculations on the vibrational quenching of HD due to collisions with H were carried out employing an accurate potential energy surface. The state-to-state cross sections for the chemical reaction HD ($v=1, \ j=0$) + H $\rightarrow$ D + H$_2$ ($v'=0, \ j'$) at collision energies between 1 and 10,000 cm$^{-1}$ are presented, and a Feshbach resonance in the low-energy regime, below the reaction barrier, is observed for the first time. The resonance is attributed to coupling with the vibrationally adiabatic potential correlating to the $v=1, \ j=1$ level of the HD molecule, and it is dominated by the contribution from a single partial wave. The properties of the resonance, such as its dynamic behavior, phase behavior, and lifetime, are discussed.