Comparison of transition state theory rate constants for internal conformational motion with those obtained from molecular dynamics simulations

The results of molecular dynamics (MD) simulations are compared to transiti on state theory estimations for formation of conformational defects in a po lymer crystal. The rates of conformational defect formation and destruction are obtained in terms of a distribution over possible conformational state s. The rate constant obtained by this method, when normalized by the number of possible defect sites, is independent of the size of the system, in app arent contrast with the results of MD simulations. The difference is interp reted in tetras of the effective temperature of the MD calculation. (C) 200 1 Elsevier Science Ltd. All rights reserved.