Structures of methyl halide dimers in supersonic jets by matrix-isolation infrared spectroscopy and quantum chemical calculations

The CH3Cl and CH3Br dimers produced by supersonic-jet expansion were directly deposited on a cold plate using a standard matrixisolation technique. Dependence of the relative intensities of the observed infrared bands on the stagnation pressure was used to assign the dimer bands appearing near the monomer bands. By a comparison of the wavenumber shifts from the monomer bands with the corresponding values obtained by quantum chemical calculations, DFT/B3LYP/6-311þþG(3pd,3df) and MP2/LanL2DZ þ fdp, the structures of CH3Cl and CH3Br dimers were determined to be a head-to-tail isomer, which is common to the CH3F and CH3I dimers determined previously by the same method. The remaining dimer bands, which could not be assigned to the head-to-tail isomer, were tentatively assigned to a head-to-head isomer in analogy with CH3I dimer. q 2004 Elsevier B.V. All rights reserved.