Reactive scattering of H2 on Cu(111) at 925 K: Effective Hartree potential vs sudden approximation

Abstract

We present new quantum dynamical results for the reactive scattering of hydrogen molecules from a Cu(111) surface at a surface temperature of 925 K. Reaction, scattering, and diffraction probabilities are compared for results obtained using both an effective Hartree potential (EfHP) and a sudden approximation approach, implemented through the static corrugation model (SCM), to include surface temperature effects. Toward this goal, we show how the SRP48 DFT-functional and an embedded atom potential perform when used to calculate copper lattice constants and thermal expansion coefficients based on lattice dynamics calculations within the quasi-harmonic approximation. The so-calculated phonons are then used in the EfHP approach to replace the normal modes of a fictitious copper cluster used in earlier work. We find that both the EfHP and SCM approaches correctly predict the reaction probability curve broadening effect when the surface temperature is increased. Similarly, results for rovibrationally elastic scattering appear to be improved, predominantly for the SCM model. The behavior of the EfHP results appears to remain much closer to that of a Born–Oppenheimer static surface approach, which excludes any surface temperature effects. Finally, for the diffraction, we show very clear attenuation effects for the SCM approach, significantly decreasing specular diffraction probabilities at 925 K surface temperature. These results demonstrate that state-of-the-art theoretical models are able to reproduce strictly quantum mechanical scattering effects with a sudden approximation model and open up interesting opportunities for further comparisons to experimental diffraction results.