A Linearized Semiclassical Dynamics Study of the Multiquantum Vibrational Relaxation of NO Scattering from a Au(111) Surface

Abstract

The vibrational relaxation of NO molecules scattering from a Au(111) surface has served as the focus of efforts to understand nonadiabatic energy transfer at metal–molecule interfaces. Experimental measurements and previous theoretical efforts suggest that multiquantal NO vibrational energy relaxation occurs via electron–hole pair excitations in the metal. Here, using a linearized semiclassical approach, we accurately predict the vibrational relaxation of NO from the νi = 3 state for different incident translational energies. We also accurately capture the central role of transient electron transfer from the metal to the molecule in mediating the vibrational relaxation process but fall short of quantitatively predicting the full extent of multiquantum relaxation for high incident vibrational excitations (νi = 16).

Vibrational energy transfer in collisions of molecules with metal surfaces

“…124,125 The approach was applied for NO (v i = 3) scattering from Au (111) qualitatively reproducing the vibrational relaxation probability dependence on incidence energy. Another interesting insight was provided by the recent work of Malpathak and Ananth, 126 where the authors employed linearized stationary-phase path-integral dynamics capable of accounting for the zero-point energy and tunneling effects in NO scattering from Au (111). They used Hamiltonian (3) to model the electronic degrees of freedom.…”