Adsorption and transformation mechanism of NO2 on NaCl(100) surface: A density functional theory study

Abstract

To understand the heterogeneous reactions between NO2 and sea salt particles in the atmosphere of coastal areas, the absorption of an NO2 molecule on the NaCl(100) surface, the dimerization of NO2 molecules and the hydrolysis of N2O4 isomers at the (100) surface of NaCl are investigated by density functional theory. Calculated results show that the most favorable adsorption geometry of isolated NO2 molecule is found to reside at the bridge site (II-1) with the adsorption energy of -14.85 kcal/mol. At the surface of NaCl(100), three closed-shell dimers can be identified as sym-O2N-NO2, cis-ONO-NO2 and trans-ONO-NO2. The reactions of H2O with sym-O2N-NO2 on the (100) surface of NaCl are difficult to occur because of the high barrier (33.79 kcal/mol), whereas, the reactions of H2O with cis-ONONO2 and trans-ONONO2 play the key role in the hydrolysis process. The product, HONO, is one of the main atmospheric sources of OH radicals which drive the chemistry of the troposphere.

Keywords: Absorption; Dimerization; Hydrolysis; NO(2); NaCl(100) surface.