Dynamics on Six-Dimensional Potential Energy Surfaces for H2/Cu(111): Corrugation Reducing Procedure versus Modified Shepard Interpolation Method and PW91 versus RPBE

We have constructed first principle based six-dimensional (6D) potential energy surfaces (PESs) describing the interaction of H2 with Cu(111) obtained by interpolation of a set of density functional theory (DFT) total energy data. The DFT calculations have been performed within the generalized gradient approximation (GGA) framework. In applying the GGA we have tested the two exchange−correlation (XC) functionals most popular in surface science, i.e., the PW91 and RPBE functionals. The interpolation of the PW91 PES has been performed using two different methods, the corrugation reducing procedure (CRP), which has been proven to be one of the most successful interpolation methods to build 6D PESs, and the modified Shepard (MS) interpolation method, a very promising method to build high dimensional (nD) PESs, which is computationally cheaper than the CRP. We show that, in spite of the difference between the CRP-PES and the MS-PES and the inaccuracies found in the latter, quantum and classical reaction and scattering probabilities obtained for both PESs are very similar. We also show that PW91 predicts higher reactivity than RPBE, due to the presence of lower energy dissociation barriers in the PW91-PES. The differences between the PW91-PES and the RPBE-PES are also reflected in the vibrational excitation and rotational excitation probabilities, and the diffraction patterns.