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Title: Quantum dynamics of hydrogen atoms on graphene. I. System-bath modeling

An accurate system-bath model to investigate the quantum dynamics of hydrogen atoms chemisorbed on graphene is presented. The system comprises a hydrogen atom and the carbon atom from graphene that forms the covalent bond, and it is described by a previously developed 4D potential energy surface based on density functional theory ab initio data. The bath describes the rest of the carbon lattice and is obtained from an empirical force field through inversion of a classical equilibrium correlation function describing the hydrogen motion. By construction, model building easily accommodates improvements coming from the use of higher level electronic structure theory for the system. Further, it is well suited to a determination of the system-environment coupling by means of ab initio molecular dynamics. This paper details the system-bath modeling and shows its application to the quantum dynamics of vibrational relaxation of a chemisorbed hydrogen atom, which is here investigated at T = 0 K with the help of the multi-configuration time-dependent Hartree method. Paper II deals with the sticking dynamics.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [1] ;  [5]
  1. Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy)
  2. Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States)
  3. School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom)
  4. Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main (Germany)
  5. (Italy)
Publication Date:
OSTI Identifier:
22489652
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 12; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; ATOMS; CHEMISORPTION; CORRELATION FUNCTIONS; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; GRAPHENE; HYDROGEN; MOLECULAR DYNAMICS METHOD; POTENTIAL ENERGY; TIME DEPENDENCE