Towards bond selective chemistry from first principles: Methane on metal surfaces

X. SHEN; A. LOZANO; DONG, W.; BUSNENGO, H.F.; X. YAN

PHYSICAL REVIEW LETTERS

AMER PHYSICAL SOC

Lugar: New York; Año: 2014 vol. 112 p. 46101 - 46105

0031-9007

Controlling bond-selective chemical reactivity is of great importance and has a broad range of applications. Here, we present a molecular dynamics study of bond selective reactivity of methane and its deuterated isotopologues (i.e. CH_{4−x}D_x, x=0,1,2,3,4) on Ni(111) and Pt(111) from first principles calculations. Our simulations allow for reproducing the full C-H bond selectivity recently achieved experimentally via mode-specific vibrational excitation and explain its origin. Moreover, we also predict the hitherto unexplored influence of the molecular translational energy on such a selectivity as well as the conditions under which the full selectivity can be realized for the a priori less active C-D bond.