Geometric Phase Effects in the Ultracold D + HD $\to$ D + HD and D + HD $\leftrightarrow$ H + D$_2$ Reactions

TL;DR

This study investigates geometric phase effects in ultracold chemical reactions involving D, HD, and H$_2$, revealing significant impact on reaction rates and scattering patterns, with potential for experimental control via nuclear spin states.

Contribution

First detailed quantum scattering calculations including geometric phase effects for ultracold D + HD and H + D$_2$ reactions, highlighting their significant influence on reaction dynamics.

Findings

Geometric phase causes up to 3 orders of magnitude change in reaction rates.

Significant alterations in differential cross sections and resonance spectra due to geometric phase.

Reaction outcomes are sensitive to nuclear spin states, enabling potential experimental control.

Abstract

The results of accurate quantum reactive scattering calculations for the D + HD($v=4$, $j=0$) $\to$ D + HD($v'$, $j'$), D + HD($v=4$, $j=0$) $\to$ H + D$_2$($v'$, $j'$) and H + D$_2$($v=4$, $j=0$) $\to$ D + HD($v'$,$j'$) reactions are presented for collision energies between $1\,\mu{\rm K}$ and $100\,{\rm K}$. The ${\it ab\ initio}$ BKMP2 PES for the ground electronic state of H$_3$ is used and all values of total angular momentum between $J=0-4$ are included. The general vector potential approach is used to include the geometric phase. The rotationally resolved, vibrationally resolved, and total reaction rate coefficients are reported as a function of collision energy. Rotationally resolved differential cross sections are also reported as a function of collision energy and scattering angle. Large geometric phase effects appear in the ultracold reaction rate coefficients which result in a significant enhancement or suppression of the rate coefficient (up to $3$ orders of magnitude) relative to calculations which ignore the geometric phase. The results are interpreted using a new quantum interference mechanism which is unique to ultracold collisions. Significant effects of the geometric phase also appear in the rotationally resolved differential cross sections which lead to a very different oscillatory structure in both energy and scattering angle. Several shape resonances occur in the $1$ - $10\,{\rm K}$ energy range and the geometric phase is shown to significantly alter the predicted resonance spectrum. The geometric phase effects depend sensitively on the nuclear spin which may provide experimentalists with the ability to control the reaction by the selection of a particular nuclear spin state.