title: The importance of accurate adiabatic interaction potentials for the correct description of electronically nonadiabatic vibrational energy transfer: a combined experimental and theoretical study of NO(v = 3) collisions with a Au(111) surface.
abstract: We present a combined experimental and theoretical study of NO(v = 3 → 3, 2, 1) scattering from a Au(111) surface at incidence translational energies ranging from 0.1 to 1.2 eV. Experimentally, molecular beam-surface scattering is combined with vibrational overtone pumping and quantum-state selective detection of the recoiling molecules. Theoretically, we employ a recently developed first-principles approach, which employs an Independent Electron Surface Hopping (IESH) algorithm to model the nonadiabatic dynamics on a Newns-Anderson Hamiltonian derived from density functional theory. This approach has been successful when compared to previously reported NO/Au scattering data. The experiments presented here show that vibrational relaxation probabilities increase with incidence energy of translation. The theoretical simulations incorrectly predict high relaxation probabilities at low incidence translational energy. We show that this behavior originates from trajectories exhibiting multiple bounces at the surface, associated with deeper penetration and favored (N-down) molecular orientation, resulting in a higher average number of electronic hops and thus stronger vibrational relaxation. The experimentally observed narrow angular distributions suggest that mainly single-bounce collisions are important. Restricting the simulations by selecting only single-bounce trajectories improves agreement with experiment. The multiple bounce artifacts discovered in this work are also present in simulations employing electronic friction and even for electronically adiabatic simulations, meaning they are not a direct result of the IESH algorithm. This work demonstrates how even subtle errors in the adiabatic interaction potential, especially those that influence the interaction time of the molecule with the surface, can lead to an incorrect description of electronically nonadiabatic vibrational energy transfer in molecule-surface collisions.
authors: Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077, Germany.
authors: Kai
authors: K
authors: Golibrzuch
authors: Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077, Germany.
authors: Pranav R
authors: PR
authors: Shirhatti
authors: Department of Natural Sciences, The Open University of Israel, Ra'anana 4353701, Israel.
authors: Igor
authors: I
authors: Rahinov
authors: Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077, Germany.
authors: Alexander
authors: A
authors: Kandratsenka
authors: Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077, Germany.
authors: Daniel J
authors: DJ
authors: Auerbach
authors: Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077, Germany.
authors: Alec M
authors: AM
authors: Wodtke
authors: Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077, Germany.
authors: Christof
authors: C
authors: Bartels
mesh_terms: D000465:Algorithms; D004583:Electrons; D004735:Energy Transfer; D017276:Friction; D005740:Gases / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D009569:Nitric Oxide / Q000737:chemistry*; D011336:Probability; D012542:Scattering, Radiation; D013499:Surface Properties; D014732:Vibration
chemical_list: D005740:Gases; D009569:Nitric Oxide; D006046:Gold