On the quantum dynamical treatment of surface vibrational modes for reactive scattering of H2 from Cu(111) at 925 K.

We construct the effective Hartree potential for H2 on Cu(111) as introduced in our earlier work [Dutta et al., J. Chem. Phys. 154, 104103 (2021), and Dutta et al., J. Chem. Phys. 157, 194112 (2022)] starting from the same gas-metal interaction potential obtained for 0 K. Unlike in that work, we now explicitly account for surface expansion at 925 K and investigate different models to describe the surface vibrational modes: (i) a cluster model yielding harmonic normal modes at 0 K and (ii) slab models resulting in phonons at 0 and 925 K according to the quasi-harmonic approximation-all consistently calculated at the density functional theory level with the same exchange-correlation potential. While performing dynamical calculations for the H2(v = 0, j = 0)-Cu(111) system employing Hartree potential constructed with 925 K phonons and surface temperature, (i) the calculated chemisorption probabilities are the highest compared to the other approaches over the energy domain and (ii) the threshold for the reaction probability is the lowest, in close agreement with the experiment. Although the survival probabilities (v' = 0) depict the expected trend (lower in magnitude), the excitation probabilities (v' = 1) display a higher magnitude since the 925 K phonons and surface temperature are more effective for the excitation process compared to the phonons/normal modes obtained from the other approaches investigated to describe the surface.