On the PES for the interaction of an H atom with an H chemisorbate on a graphenic platelet

Motivated by the problem of H(2) formation in diffuse clouds of the interstellar medium (ISM), we study the effect of including van der Waals-type corrections in DFT calculations on the entrance PES of the Eley-Rideal reaction H(b) + H(a)-GR → H(b)-H(a) + GR for a graphenic surface GR. The present calculations make use of the PBE-D3 dispersion corrected functional of Grimme et al. (2010) and are carried out on cluster models of graphenic surfaces: C(24)H(12) and C(54)H(18). To assess the soundness of the chosen functional we start by revisiting the H-GR adsorption potential. We find a satisfactory on top physisorption well (43-48 meV) correctly located at an H-GR distance of 3 Å. We then revisit the H(b)-H(a)-GR system using both the PW91 and PBE functionals. Our calculations do not reproduce the tiny potential barrier reported earlier for large H(b)distances from the surface. The barrier in the calculations of Sidis et al. (2000) and Morisset et al. (2003, 2004) has been traced to their previous use of an LSDA + POSTSCF PW91 procedure rather than the genuine PW91 one. The new PBE-D3 PES for the H(b)-H(a)-GR system is reported as a function of the H(b) distance to the surface and its impact parameter relative to the H(a) chemisorbate for the so-called "fixed puckered" ("diabatic" or "sudden") approach. The results are discussed in relation to recent experimental and theoretical work.