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Specific rate constants,  k ( E , J ), and thermal capture rate constants,  k  cap ( T ), are determined by statistical adiabatic channel model/classical trajectory (SACM/CT) calculations for unimolecular dissociation and the reverse association reactions of representative polyatomic molecular ions. Simple short-range valence/long-range ion-induced dipole model potentials without reverse barriers have been employed, using the reactions C 8 H 10  +  ⇔ C 7 H 7  +  + CH 3  and C 9 H 12  +  ⇔ C 7 H 7  +  + C 2 H 5  as illustrative examples. Simplified representations of  k ( E ) and  k  cap ( T ) from rigid activated complex Rice–Ramsperger–Kassel–Marcus (RRKM) theory are compared with the SACM/CT treatment and with experimental results. The Massey parameters of the transitional mode dynamics, for the systems considered, are smaller than unity such that their dynamics is nonadiabatic while the dynamics of the conserved modes is adiabatic. Because of the long-range/short-range switching character of the potential, simple rigid activated complex RRKM theory cannot be used without modifications. The effects of a shifting of the effective bottle-neck of the dynamics with increasing energy towards smaller interfragment distances in the present cases are amplified by a shift into a range of increasing anisotropy of the potential. As a consequence, the thermal capture rate constants markedly decrease with increasing temperature.

zeitschrift für physikalische chemie

Classical Trajectory and Statistical Adiabatic Channel Study of the Dynamics of Capture and Unimolecular Bond Fission. VII. Thermal Capture and Specific Rate Constants  k ( E , J ) for the Dissociation of Molecular Ions