Journal of Physical Chemistry A, Vol.119, No.50, 12146-12158, 2015
Performance of a Non-Local van der Waals Density Functional on the Dissociation of H-2 on Metal Surfaces
van der Waals functionals have recently been applied to obtain a potential energy surface to describe the dissociation of H-2 on Ru(0001), where an improvement was found for computed reaction probabilities compared to experiment, which could not be achieved with the use of other exchange-correlation functionals. It is, however, not yet clear to what extent van der Waals functionals give a better description of other moleculemetal surface systems. In this study, the optPBE-vdW-DF functional is compared to the SRP48 functional, which was originally fitted to describe the dissociation of H-2 on Cu(111), in terms of the resulting potential energy surfaces and results of quasi-classical dynamics calculations and their agreement with experiment for different H-2-metal surface systems. It is found that overall the optPBE-vdW-DF functional yields potential energy surfaces that are very similar to potential energy surfaces computed with the SRP48 functional. In dynamics calculations the optPBE-vdW-DF functional gives a slightly better description of molecular beam experiments. Also a different dependence of reaction on the rotational quantum number J is found, which is in better agreement with experimental data for H-2 dissociation on Cu(111). The vibrational efficacy is found to be relatively insensitive to which of the two functionals is chosen.