Mode-specificity and transition state-specific energy redistribution in the chemisorption of CH4 on Ni{100}

Sacchi, M., Wales, D. J. and Jenkins, S. J. (2012) Mode-specificity and transition state-specific energy redistribution in the chemisorption of CH4 on Ni{100}. Physical Chemistry Chemical Physics, 14 (45). pp. 15879-15887. ISSN 1463-9076 doi: 10.1039/c2cp42345f

Abstract/Summary

We have investigated methane (CH4) dissociative chemisorption on the Ni{100} surface by first-principles molecular dynamics (MD) simulations. Our results show that this reaction is mode-specific, with the n1 state being the most strongly coupled to efficient energy flow into the reaction coordinate when the molecule reaches the transition state. By performing MD simulations for two different transition state (TS) structures we provide evidence of TS structure-specific energy redistribution in methane chemisorption. Our results are compared with recently reported state-resolved measurement of methane adsorption probability on nickel surfaces, and we find that a strong correlation exists between the highest vibrational efficacy measured on Ni{100} for the n1 state and the calculated highest fractional vibrational energy content in this mode.