Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction.
Although important to heterogeneous catalysis, the ability to accurately model reactions of polyatomic molecules with metal surfaces has not kept pace with developments in gas phase dynamics. Partnering the specific reaction parameter (SRP) approach to density functional theory with ab initio molecular dynamics (AIMD) extends our ability to model reactions with metals with quantitative accuracy from only the lightest reactant, H2, to essentially all molecules. This is demonstrated with AIMD calculations on CHD3 + Ni(111) in which the SRP functional is fitted to supersonic beam experiments, and validated by showing that AIMD with the resulting functional reproduces initial-state selected sticking measurements with chemical accuracy (4.2 kJ/mol ≈ 1 kcal/mol). The need for only semilocal exchange makes our scheme computationally tractable for dissociation on transition metals.
Leiden Institute of Chemistry, Leiden University , Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Francesco
F
Nattino
Leiden Institute of Chemistry, Leiden University , Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Davide
D
Migliorini
Leiden Institute of Chemistry, Leiden University , Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Geert-Jan
GJ
Kroes
Department of Chemistry and W. M. Keck Foundation Laboratory for Materials Chemistry, Tufts University , Medford, Massachusetts 02155, United States.
Eric
E
Dombrowski
Department of Chemistry and W. M. Keck Foundation Laboratory for Materials Chemistry, Tufts University , Medford, Massachusetts 02155, United States.
Eric A
EA
High
Department of Chemistry & Biochemistry, Loyola University Chicago , 1068 West Sheridan Road, Chicago, Illinois 60660, United States.
Daniel R
DR
Killelea
Department of Chemistry and W. M. Keck Foundation Laboratory for Materials Chemistry, Tufts University , Medford, Massachusetts 02155, United States.
Arthur L
AL
Utz