Vibrationally Mode-Specific Molecular Energy Transfer to Surface Electrons in Metastable Formaldehyde Scattering from Cesium-Covered Au(111).

Nonadiabatic interaction of adsorbate nuclear motion with the continuum of electronic states is known to affect the dynamics of chemical reactions at metal surfaces. A large body of work has probed the fundamental mechanisms of such interactions for atomic and diatomic molecules at surfaces. In polyatomic molecules, the possibility of mode-specific damping of vibrational motion due to the effects of electronic friction raises the question of whether such interactions could profoundly affect the outcome of chemistry at surfaces by selectively removing energy from a particular intramolecular adsorbate mode. However, to date, there have not been any fundamental experiments demonstrating nonadiabatic electron-vibration coupling in a polyatomic molecule at a surface. In this work, we scatter excited metastable formaldehyde and formaldehyde-d2 from a low work function surface and detect ejected exoelectrons that accompany molecular relaxation. The exoelectron ejection efficiency exhibits a strong dependence on the vibrational mode that is excited: out-of-plane bending excitation (ν4) leads to significantly more exoelectrons than does CO stretching excitation (ν2). The results provide clear evidence for mode-specific energy transfer from vibration to surface electrons.