Quantum scattering of hot H/D on CO$_2$: Cross sections and rate coefficients for planetary atmospheres and their evolution
Collisions between hot hydrogen atoms and CO$_2$ play a central role in energy transfer and atmospheric escape in CO$_2$-rich planetary atmospheres. We present quantum mechanical $j_z$-conserving coupled-states calculations of state-resolved cross sections for H/D--CO$_2$ collisions at energies up to 5~eV, benchmarked to within 7\% of close-coupling results. Scattering is strongly forward-peaked, yielding momentum-transfer cross sections substantially smaller than commonly assumed: mass-scaling from O/C--CO$_2$ systems overestimates H--CO$_2$ total cross sections by factors of 30--45, while existing empirical fits underestimate the low-energy regime by up to $\sim$45\%. Isotopic substitution (H/D) produces energy-dependent differences of up to 35\% at $E<0.1$~eV, invalidating uniform scaling approaches for D/H fractionation. Maxwellian-averaged rate coefficients derived from our cross sections are significantly smaller than mass-scaled values, implying reduced H--CO$_2$ energy transfer efficiency. In atmospheric escape modelling, these revisions can shift Martian exobase altitudes by 10--20~km, leading to order-unity changes in thermal escape rates, and have implications for hydrogen loss in early CO$_2$-dominated planetary atmospheres. Our results provide essential quantum-mechanical inputs for revisiting atmospheric evolution scenarios on Mars, early Earth, and CO$_2$-rich exoplanets.