An exact formulation of hyperdynamics simulations

We introduce a new formula for the acceleration weight factor in the hyperdynamics simulation method, the use of which correctly provides an exact simulation of the true dynamics of a system. This new form of hyperdynamics is valid and applicable where the transition state theory (TST) is applicable and also where the TST is not applicable. To illustrate this new formulation, we perform hyperdynamics simulations for four systems ranging from one degree of freedom to 591 degrees of freedom: (1) We first analyze free diffusion having one degree of freedom. This system does not have a transition state. The TST and the original form of hyperdynamics are not applicable. Using the new form of hyperdynamics, we compute mean square displacement for a range of time. The results obtained agree perfectly with the analytical formula. (2) Then we examine the classical Kramers escape rate problem. The rate computed is in perfect agreement with the Kramers formula over a broad range of temperature. (3) We also study another classical problem: Computing the rate of effusion out of a cubic box through a tiny hole. This problem does not involve an energy barrier. Thus, the original form of hyperdynamics excludes the possibility of using a nonzero bias and is inappropriate. However, with the new weight factor formula, our new form of hyperdynamics can be easily implemented and it produces the exact results. (4) To illustrate applicability to systems of many degrees of freedom, we analyze diffusion of an atom adsorbed on the (001) surface of an fcc crystal. The system is modeled by an atom on top of a slab of six atomic layers. Each layer has 49 atoms. With the bottom two layers of atoms fixed, this system has 591 degrees of freedom. With very modest computing effort, we are able to characterize its diffusion pathways in the exchange-with-the-substrate and hop-over-the-bridge mechanisms.     

Transition rate prefactors for systems of many degrees of freedom

When a minimum on the potential energy surface is surrounded by multiple saddle points with similar energy barriers, the transition pathways with greater prefactors are more important than those that have similar energy barriers but smaller prefactors. In this paper, we present a theoretical formulation for the prefactors, computing the probabilities for transition paths from a minimum to its surrounding saddle points. We apply this formulation to a system of 2 degrees of freedom and a system of 14 degrees of freedom. The first is Brownian motion in a two-dimensional potential whose global anharmonicities play a dominant role in determining the transition rates. The second is a Lennard-Jones (LJ) cluster of seven particles in two dimensions. Low lying transition states of the LJ cluster, which can be reached directly from a minimum without passing through another minimum, are identified without any presumption of their characteristics nor of the product states they lead to. The probabilities are computed for paths going from an equilibrium ensemble of states near a given minimum to the surrounding transition states. These probabilities are directly related to the prefactors in the rate formula. This determination of the rate prefactors includes all anharmonicities, near or far from transition states, which are pertinent in the very sophisticated energy landscape of LJ clusters and in many other complex systems.