Transferability of the SRP32-vdW specific reaction parameter functional to CHD3 dissociation on Pt(110)-(2 × 1)

Stepped transition metal surfaces, including the reconstructed Pt(110)-(2 × 1) surface, can be used to model the effect of line defects on cata- lysts. We present a combined experimental and theoretical study of CHD3 dissociation on this surface. Theoretical predictions for the initial sticking coefficients, S0, are obtained from ab initio molecular dynamics calculations using the specific reaction parameter (SRP) approach to density functional (DF) theory, while the measured sticking coefficients were obtained using the King and Wells method. The SRP DF used here had been previously derived for methane dissociation on Pt(111) so that the experiments test the transferability of this SRP DF to methane + Pt(110)-(2 × 1). The agreement between the experimental and calculated S0 is poor, with the average energy shift between the theoretical and measured reactivities being 20 kJ/mol. There are two factors which may contribute to this difference, the first of which is that there is a large uncertainty in the calculated sticking coefficients due to a large number of molecules being trapped on the surface at the end of the 1 ps propagation time. The second is that the SRP32-vdW functional may not accurately describe the Pt(110)-(2 × 1) surface. At the lowest incident energies considered here, Pt(110)-(2 × 1) is more reactive than the flat Pt(111) surface, but the situation is reversed at incident energies above 100 kJ/mol.

Publié dans:
The Journal of Chemical Physics, 150, 12, 124702
Mar 25 2019
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 Notice créée le 2019-03-26, modifiée le 2019-03-26

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