부산대학교 도서관

The ion–molecule reaction CH3++CH3CN is known to have an association channel leading to CH3CNCH3+ in competition with the exothermic binary channels H2CN++C2H4 and C2H5++HCN. This reaction has been modeled using a master equation treatment incorporating weak collisions. The parameters required for the Rice–Ramsberger–Kassel–Marcus (RRKM) treatment have been found from an ab initio investigation of the CH3+/CH3CN energy surface. A means of including capture rate coefficients in the RRKM approach is developed, in which only the hindered dipole rotation is coupled with the reaction coordinate at large separations. Existing experimental data from ion cyclotron resonance (ICR) spectroscopy and a selected ion flow tube are fitted by the model in the pressure range 10-7–0.3 Torr. The low pressure experimental results are accounted for by weak collisions of the complex with the bath gas (when M=He, <ΔEdown>= and <ΔRdown>=∼100 cm-1) corresponding to a collision efficiency β=0.05 for M=He and 0.14 for M=CH3CN. Unimolecular rate coefficients for the (CH3CNCH3+)* complex are calculated for all product channels at a range of temperatures from 300 to 600 K. The rate coefficient for radiative stabilization was found to be 225 s-1 at the conditions of the ICR experiment. The average lifetime of the complex was calculated to vary between 29 μs at 600 K to 0.47 ms at 300 K and the termolecular association rates from 3.4×10-24–9.8×10-23 cm6 s-1 (M=He) and from 6.7×10-23–2.2×10-21 cm6 s-1 (M=CH3CN) over the temperature range 600–300 K. [ABSTRACT FROM AUTHOR]