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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 andmore » 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.« less

Authors:
; ; ; ;  [1];  [2];  [1]
  1. Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077 (Germany)
  2. Department of Natural Sciences, The Open University of Israel, Ra'anana 4353701 (Israel)
Publication Date:
OSTI Identifier:
22255245
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 4; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALGORITHMS; ANGULAR DISTRIBUTION; COLLISIONS; DENSITY FUNCTIONAL METHOD; DETECTION; ELECTRONS; ENERGY TRANSFER; HAMILTONIANS; INTERACTIONS; NITRIC OXIDE; PROBABILITY; QUANTUM STATES; RELAXATION; SCATTERING; SIMULATION; SURFACES

Citation Formats

Golibrzuch, Kai, Shirhatti, Pranav R., Kandratsenka, Alexander, Wodtke, Alec M., Bartels, Christof, Max Planck Institute for Biophysical Chemistry, Göttingen 37077, Rahinov, Igor, Auerbach, Daniel J., Max Planck Institute for Biophysical Chemistry, Göttingen 37077, and Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106. 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. United States: N. p., 2014. Web. doi:10.1063/1.4861660.
Golibrzuch, Kai, Shirhatti, Pranav R., Kandratsenka, Alexander, Wodtke, Alec M., Bartels, Christof, Max Planck Institute for Biophysical Chemistry, Göttingen 37077, Rahinov, Igor, Auerbach, Daniel J., Max Planck Institute for Biophysical Chemistry, Göttingen 37077, & Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106. 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. United States. doi:10.1063/1.4861660.
Golibrzuch, Kai, Shirhatti, Pranav R., Kandratsenka, Alexander, Wodtke, Alec M., Bartels, Christof, Max Planck Institute for Biophysical Chemistry, Göttingen 37077, Rahinov, Igor, Auerbach, Daniel J., Max Planck Institute for Biophysical Chemistry, Göttingen 37077, and Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106. Tue . "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". United States. doi:10.1063/1.4861660.
@article{osti_22255245,
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},
author = {Golibrzuch, Kai and Shirhatti, Pranav R. and Kandratsenka, Alexander and Wodtke, Alec M. and Bartels, Christof and Max Planck Institute for Biophysical Chemistry, Göttingen 37077 and Rahinov, Igor and Auerbach, Daniel J. and Max Planck Institute for Biophysical Chemistry, Göttingen 37077 and Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106},
abstractNote = {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.},
doi = {10.1063/1.4861660},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 4,
volume = 140,
place = {United States},
year = {2014},
month = {1}
}