Selective IR-induced isomerization of 1,2-dichloropropane isolated in xenon matrix

Abstract

The conformations of monomeric 1,2-dichloropropane isolated in low temperature xenon matrix were characterized experimentally using FTIR spectroscopy. The interpretation of the experimental spectra was aided by ab initio MP2/6-311++G(3df,3pd) calculations. Relative energies of three structures, differing by the orientation of the Cl−C−C−Cl dihedral angle, fall within 0–6 kJ mol −1 range. The spectral signatures of all three conformers were identified experimentally. Infrared irradiation of the matrix isolated compound resulted in selective conversion of the most stable Trans conformer into the higher energy Gauche+ rotamer, while the Gauche− conformer remained unaffected. This result was interpreted in terms of calculated energy barriers and dipole moments.