Low temperature measurements of the rate of association to benzene dimers in helium

摘要

The association of benzene molecules to form dimers has been studied at temperatures between 15 and 123 K in a CRESU (Cinetique de Reactions en Ecoulement Supersonique Uniforme) apparatus with helium as the buffer gas. Second-order rate coefficients (k(2)) for the formation of dimers have been determined for temperatures between 15 and 88 K. The effective third-order rate coefficients (no study of fall off behavior has been undertaken) obtained by dividing the values of k(2) by [He] show a strong negative temperature dependence. Further evidence for the formation of dimers at critical concentrations of benzene has been obtained from a study of the CH + C6H6 reaction and from LIF spectra. Modelling calculations indicate that any systematic errors in the results arising from the formation of higher oligomers are small. Based on a model in which it is assumed that the benzene molecules in the dimer are free to rotate, third-order rate coefficients have been calculated for dimerization and are in good agreement with the experimental values for T greater than or equal to 30 K, where effects of falloff should not be too great. (C) 2000 American Institute of Physics. [S0021-9606(00)01710-4]. [References: 46]