Rate Constants

Wednesday, July 25, 2007 - 11:00am - 12:00pm
EE/CS 3-180
Giovanni Ciccotti (Università di Roma La Sapienza), Mark Tuckerman (New York University)
The linear response theory formulation of a rate constan as a suitable time correlation function; its representation via the transition state theory (TST) term and the transmission coefficient. Calculation of the TST term via the blue-moon approach. i.e. impose a reaction coordinate as a constraint, compute its associated free energy and, by exponentiation, compute the associated probability. Use the unbiased constrained ensemble to generate a proper ensemble of reactive trajectories and compute the transmission coeffcient. The product of the TST term times the transmission coefficient provides the rate constant.