English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  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.

Golibrzuch, K., Shirhatti, P. R., Rahinov, I., Kandratsenka, A., Auerbach, D. J., Wodtke, A. M., et al. (2014). 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. The Journal of Chemical Physics, 140(4): 044701. doi:10.1063/1.4861660.

Item is

Basic

show hide
Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0017-C2DB-3 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0028-9495-4
Genre: Journal Article

Files

show Files
hide Files
:
1949913.pdf (Publisher version), 2MB
Name:
1949913.pdf
Description:
-
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-

Creators

show
hide
 Creators:
Golibrzuch, K.1, Author              
Shirhatti, P. R.1, Author              
Rahinov, I., Author
Kandratsenka, A.2, Author              
Auerbach, D. J.1, Author              
Wodtke, A. M.1, Author              
Bartels, C.1, Author              
Affiliations:
1Department of Dynamics at Surfaces, MPI for biophysical chemistry, Max Planck Society, ou_578600              
2Research Group of Reaction Dynamics, MPI for biophysical chemistry, Max Planck Society, ou_578601              

Content

show
hide
Free keywords: -
 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.

Details

show
hide
Language(s): eng - English
 Dates: 2014-01-222014-01-28
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1063/1.4861660
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: The Journal of Chemical Physics
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: -
Pages: 14 Volume / Issue: 140 (4) Sequence Number: 044701 Start / End Page: - Identifier: -