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The effect of surface mode vibrations on the reactive scattering of D2, initialized in the ground rovibrational state (v = 0, j = 0), from a Cu(111) surface is investigated for different surface temperature situations. We adopt a time and temperature dependent effective Hamiltonian [Dutta et al., J. Chem. Phys. 154, 104103 (2021)] constructed by combining the linearly coupled many oscillator model [Sahoo et al., J. Chem. Phys. 136, 084306 (2012)] and the static corrugation model [M. Wijzenbroek and M. F. Somers, J. Chem. Phys. 137, 054703 (2012)] potential within the mean-field approach. Such an effective Hamiltonian is employed for six-dimensional quantum dynamical calculations to obtain temperature dependent reaction and state-to-state scattering probability profiles as a function of incidence energy of colliding D2 molecules. As reported in the experimental studies, the movements of surface atoms modify the dissociative scattering dynamics at higher surface temperature by exhibiting vibrational quantum and surface atoms' recoil effects in the low and high collision energy domains, respectively. Finally, we compare our present theoretical results with the experimental and other theoretical outcomes, as well as discuss the novelty of our findings. [ABSTRACT FROM AUTHOR]

The effect of surface atom vibrations on H2 scattering from a Cu(111) surface at different temperatures is being investigated for hydrogen molecules in their rovibrational ground state (v = 0, j = 0). We assume weakly correlated interactions between molecular degrees of freedom and surface modes through a Hartree product type wavefunction. While constructing the six-dimensional effective Hamiltonian, we employ (a) a chemically accurate potential energy surface according to the static corrugation model [M. Wijzenbroek and M. F. Somers, J. Chem. Phys. 137, 054703 (2012)]; (b) normal mode frequencies and displacement vectors calculated with different surface atom interaction potentials within a cluster approximation; and (c) initial state distributions for the vibrational modes according to Bose–Einstein probability factors. We carry out 6D quantum dynamics with the so-constructed effective Hamiltonian and analyze sticking and state-to-state scattering probabilities. The surface atom vibrations affect the chemisorption dynamics. The results show physically meaningful trends for both reaction and scattering probabilities compared to experimental and other theoretical results. [ABSTRACT FROM AUTHOR]

[Display omitted] The effect of surface temperature on the scattering and dissociation processes of D 2 (v = 0, j = 0)/D 2 (v = 0, j = 2) on Cu(111) metal plane is investigated by formulating a time and temperature dependent effective Hamiltonian within mean-field approach, where the molecular degrees of freedom and surface mode vibrations are assumed to be weakly coupled with each other. While constructing such effective Hamiltonian with a Hartree product type wavefunction, we incorporate: (i) an operator algebra method to circumscribe higher order-quadratic (anharmonic) molecular DOFs-surface modes couplings over the linear coupling case implemented previously [Adhikari and coworkers, J. Chem. Phys. 154 , 104103 (2021)]; (ii) surface temperature by considering Bose–Einstein or Maxwell–Boltzmann probability factors for the initial state distribution of the surface vibrational modes. Finally, a six-dimensional (6D) quantum dynamical (QD) calculation is performed with such newly formulated effective Hartree potential and calculated transition/dissociation probabilities at various surface temperature situations. The quadratic (anharmonic) molecular DOFs-surface modes couplings modify the reaction and transition probabilities substantially with change of surface temperature, which indicates the crucial role of surface mode vibrations on the molecule-surface scattering phenomena. [ABSTRACT FROM AUTHOR]