Deuteration of ammonia with D atoms on oxidized partly ASW covered graphite surface

The deuteration of ammonia by D atoms has been investigated experimentally in the sub-monolayer regime on realistic analogues of interstellar dust grain surfaces. About 0.8 monolayer of solid NH3 was deposited on top of an oxidized graphite surface held at 10 K, partly covered with ASW ice. Ammonia ice is subsequently exposed to D atoms for different exposure times using a differentially pumped beam-line. The deuteration experiments of ammonia were carried out by mass spectroscopy and temperature programmed desorption (TPD) technique. The experimental results showed the formation of three isotopologue ammonia species by direct exothermic H-D substitution surface reactions: NH3+D->NH2D+H, NH2D+D->NHD2+H, and NHD2+D->ND3+H. The formation of the deuterated isotopologues NH2D, NHD2, and ND3 at low surface temperature (10 K) is likely to occur through quantum tunneling process on the oxidized graphite surface. A kinetic model taking into account the diffusion of D atoms on the surface is developed to estimate the width and the hight of the activation energy barriers for the successive deuteration reactions of ammonia species by D atoms. Identical control experiments were performed using CH3OH and D atoms. The deuteration process of solid methanol is ruled by H abstraction and D addition mechanism, and is almost five orders of magnitude faster than ammonia deuteration process.