Transition state theory and dynamical corrections in ergodic systems

Fabio A Tal, Eric Vanden-Eijnden
2006 Nonlinearity  
The results of transition state theory and the so-called Bennett-Chandler procedure are derived rigorously in the general context of ergodic dynamical systems defined by a vector field on a Riemannian manifold. This allows one to give a new perspective on the Bennett-Chandler procedure to compute the dynamical corrections to the TST transition frequency. Hamiltonian dynamical systems are also considered as a special case. The so-called Marcus formula is re-derived and a new criterion for
more » ... ly partioning the configuration space so as to minimize the transition rate is obtained. Finally we discuss new estimates for the error TST introduces if the dynamical corrections are not accounted for.
doi:10.1088/0951-7715/19/2/014 fatcat:dopen6bb4vdqzolae5f7e5nzra