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Choosing adiabaticity parameters

In this section, a protocol for choosing the parameters for the reaction coordinate temperature and mass in order to ensure that adiabaticity is maintained and that phase space is properly sampled will be discussed. The temperature of the reaction coordinate needs to be close to the barrier height of the bare potential divided by Boltzmann's constant, however, as Fig. 4 shows, it is possible for it to be greater or less than this value. In cases where free energy barriers are expected to be higher than the bare potential barrier, a larger temperature will likely be needed. In general, higher temperatures work as well but require higher masses. Typically, a short run is sufficient to determine if the reaction coordinate is undergoing frequent barrier crossing events. Note that the higher the temperature of the reaction coordinate, the larger will be the required mass separation between the reaction coordinate and other modes in order to maintain adiabaticity. The mass of the reaction coordinate, which controls the adiabaticity, needs to be chosen such that the characteristic frequency of the reaction coordinate motion is small compared to that of the remaining degrees of freedom. In general, it is possible to provide estimates of these frequencies for the physical system under consideration. Generally, it is found that a frequency scale separation of approximately 2-4 is sufficient to maintain satisfactory adiabatic separation. As is clear from the parameters used in the two examples of Sec. 3, such frequency scale separations lead to the most accurate results for the shortest simulation runs. Note that once a mass scale separation for the reaction coordinate is chosen, the time scale for the evolution of the dynamical thermostats needs to be adjusted accordingly (see Refs. [12, 13]).



Mark Tuckerman
Mon Mar 26 04:23:46 EST 2001