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

被引:41
作者
Golibrzuch, Kai [1 ,2 ]
Shirhatti, Pranav R. [1 ,2 ]
Rahinov, Igor [3 ]
Kandratsenka, Alexander [1 ,2 ]
Auerbach, Daniel J. [1 ,2 ,4 ]
Wodtke, Alec M. [1 ,2 ]
Bartels, Christof [1 ,2 ]
机构
[1] Univ Gottingen, Inst Phys Chem, D-37077 Gottingen, Germany
[2] Max Planck Inst Biophys Chem, D-37077 Gottingen, Germany
[3] Open Univ Israel, Dept Nat Sci, IL-4353701 Raanana, Israel
[4] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA
关键词
BORN-OPPENHEIMER APPROXIMATION; METAL-SURFACES; INELASTIC-SCATTERING; MOLECULAR-DYNAMICS; NO SCATTERING; EXCITATION; CO; CHEMISTRY; LIFETIME; AG(111);
D O I
10.1063/1.4861660
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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. (C) 2014 AIP Publishing LLC.
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页数:14
相关论文
共 46 条
[1]   LOCALIZED MAGNETIC STATES IN METALS [J].
ANDERSON, PW .
PHYSICAL REVIEW, 1961, 124 (01) :41-&
[2]   Energy transfer at metal surfaces: the need to go beyond the electronic friction picture [J].
Bartels, Christof ;
Cooper, Russell ;
Auerbach, Daniel J. ;
Wodtke, Alec M. .
CHEMICAL SCIENCE, 2011, 2 (09) :1647-1655
[3]   Observation of orientation-dependent electron transfer in molecule-surface collisions [J].
Bartels, Nils ;
Golibrzuch, Kai ;
Bartels, Christof ;
Chen, Li ;
Auerbach, Daniel J. ;
Wodtke, Alec M. ;
Schaefer, Tim .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2013, 110 (44) :17738-17743
[4]   ULTRAFAST INFRARED RESPONSE OF ADSORBATES ON METAL-SURFACES - VIBRATIONAL LIFETIME OF CO/PT(111) [J].
BECKERLE, JD ;
CASASSA, MP ;
CAVANAGH, RR ;
HEILWEIL, EJ ;
STEPHENSON, JC .
PHYSICAL REVIEW LETTERS, 1990, 64 (17) :2090-2093
[5]   THERMAL SCATTERING OF X-RAYS BY CRYSTALS .1. DYNAMICAL FOUNDATION [J].
BEGBIE, GH ;
BORN, M .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1947, 188 (1013) :179-188
[6]   THERMAL SCATTERING OF X-RAYS BY CRYSTALS .2. THE THERMAL SCATTERING OF THE FACE-CENTRED CUBIC AND THE CLOSE-PACKED HEXAGONAL LATTICES [J].
BEGBIE, GH .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1947, 188 (1013) :189-208
[7]  
Billing G. D, 2000, Dynamics of Molecule Surface Interaction
[8]   Femtosecond surface vibrational spectroscopy of CO adsorbed on Ru(001) during desorption [J].
Bonn, M ;
Hess, C ;
Funk, S ;
Miners, JH ;
Persson, BNJ ;
Wolf, M ;
Ertl, G .
PHYSICAL REVIEW LETTERS, 2000, 84 (20) :4653-4656
[9]  
Born M., 2006, Annalen der Physik, V389, P457
[10]   INFRARED FLUORESCENCE FROM A MONOLAYER OF CO ON NACL(100) [J].
CHANG, HC ;
EWING, GE .
PHYSICAL REVIEW LETTERS, 1990, 65 (17) :2125-2128