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

Chadwick, H.J.; Gutiérrez-González, A.; Beck, R.D.; Kroes, G.-J.

doi:doi:10.1063/1.5081005

Stepped transition metal surfaces, including the reconstructed Pt(110)-(2 × 1) surface, can be used to model the effect of line defects on catalysts. 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,...Show moreStepped transition metal surfaces, including the reconstructed Pt(110)-(2 × 1) surface, can be used to model the effect of line defects on catalysts. 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.Show less

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