Ab initio study of the adsorption of CO(2) on functionalized benzenes.

The interaction of carbon dioxide with a series of functionalized aromatic molecules was studied by using quantum mechanical methods (MP2), to examine the effect of the substituent on the adsorption of CO2 . Several different initial configurations of CO2 were taken into account for each functionalized benzene to locate the energetically most favorable configuration. To get a better estimation of the binding energies, we applied an extrapolation scheme to approach the complete basis set. CH2 N3 -, COOH-, and SO3 H-functionalized benzenes were found to have the strongest interaction with CO2 , and the corresponding binding energies were calculated to be -3.62, -3.65, and -4.3 kcal mol(-1) , respectively. Electrostatic potential maps of the functionalized benzenes and electron redistribution density plots of the complexes were also created to get a better insight into the nature of the interaction of CO2 with the functionalized benzenes. The functional groups that were examined can be potentially incorporated in organic bridging molecules that connect the inorganic corners in MOF.