Accession Number : ADA183977

Title :   Monte Carlo Simulation of Primitive Atom-Transfer Reactions in Solution.

Descriptive Note : Technical rept.,

Corporate Author : OAKLAND UNIV ROCHESTER MICH DEPT OF CHEMISTRY

Personal Author(s) : Schmidt,P P ; Blum,Lester

PDF Url : ADA183977

Report Date : Jul 1987

Pagination or Media Count : 50

Abstract : This work develops a computational algorithm which combines saddle point and Metropolis/Monte Carlo optimization to investigate reactions in solution; the reactions involve atom transfer on an adiabatic potential energy surface. The value of the rate constant is calculated in the form of the simple Arrhenius equation for the jump rate nu, -omega exp (-(E superscript F -E sub o/kT), in which E superscript F is the average energy of the transition state, E sub o is the average energy of the initial state, and omega is the average frequency of passage through the transition state. Individual configurations in the Metropolis sample allow either for passage of the reactive species over the top of the barrier or tunnelling through the barrier. The average frequency omega reflects this situation. Because the Metropolis sampling method deals with discrete collections of particles, with specified forces of interaction, the transfer frequencies for over-the-top of the barrier and tunnel transfers can be determined in terms of the actual interactions used instead of using non-specific, model potential energy functions for the barrier.

Descriptors :   *ELECTRON TRANSFER, *SOLUTIONS(MIXTURES), ADIABATIC CONDITIONS, POTENTIAL ENERGY, SURFACES, COLLECTION, PARTICLES, MODELS, RATES, ATOMS, TRANSFER, ALGORITHMS, COMPUTATIONS, MONTE CARLO METHOD, SIMULATION, REACTIVITIES, TRANSITIONS, TUNNELING(ELECTRONICS)

Subject Categories : Physical Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE