Six-dimensional state-to-state quantum dynamics of H2/D2 scattering from Cu(100): Validity of site-averaging model

Abstract

Six-dimensional quantum dynamics calculations for the state-to-state scattering of H2/D2 on the rigid Cu(100) surface have been carried out using a time-dependent wave packet approach, based on an accurate neural network potential energy surface fit for thousands of density functional theory data computed with the optPBE-vdW density functional. The present results are compared with previous theoretical and experimental ones regarding to the rovibrationally (in)elastic scattering of H2 and D2 from Cu(100). In particular, we test the validity of the site-averaging approximation in this system by which the six-dimensional (in)elastic scattering probabilities are compared with the weighted average of four-dimensional results over fifteen fixed sites. Specifically, the site-averaging model reproduces vibrationally elastic scattering probabilities quite well, though less well for vibrationally inelastic results at high energies. These results support the use of the site-averaging model to reduce computational costs in future investigations on the state-to-state scattering dynamics of heavy diatomic or polyatomic molecules from metal surfaces, where full-dimensional calculations are too expensive.