Energy Partitioning in Dust-catalyzed $\mathrm{H_2}$ and HD Formation Revealed by Molecular Simulations Considering Nuclear Quantum Effects

Abstract

Molecular hydrogen formation on interstellar dust grains is a key surface process in the interstellar medium, but the redistribution of the recombination energy between the substrate and the nascent molecule remains poorly understood. Here, we use ring-polymer molecular dynamics (RPMD) with a machine-learning force field to investigate energy partitioning during $\mathrm{H_2}$ and $\mathrm{HD}$ formation on graphene at $T=25, 50$ and $100 \mathrm{K}$. We focus on the chemisorbed-H recombination pathway previously identified as the dominant low-temperature channel on bare graphitic surfaces when nuclear quantum effects are included. The desorbing molecule retains the major fraction of the effective surface-mediated released energy, while graphene absorbs a smaller but non-negligible part. This molecular retention fraction is nearly temperature-independent over the investigated range. In contrast, the post-formation molecular kinetic-energy distribution changes more strongly with temperature: rovibrational motion dominates at low temperature, whereas center-of-mass translation becomes increasingly important at $100 \mathrm{K}$. $\mathrm{H_2}$ and $\mathrm{HD}$ exhibit broadly similar total energy retention, with only modest isotope-dependent differences in their internal kinetic-energy partitioning. These results provide an energy-resolved microscopic picture of surface-mediated energy redistribution in $\mathrm{H_2}$/$\mathrm{HD}$ formation, with implications for formation-pumping signatures in high-excitation $\mathrm{H_2}$ lines, vibrationally excited $\mathrm{H_2}$ chemistry, and collisional excitation of coexisting molecules by translationally hot nascent $\mathrm{H_2}$ in cold interstellar gas.