A chain of states method for investigating infrequent event processes occurring in multistate, multidimensional systems

Sevick, E. M.; Bell, A. T.; Theodorou, D. N.
February 1993
Journal of Chemical Physics;2/15/1993, Vol. 98 Issue 4, p3196
Academic Journal
This paper describes novel numerical methods for constructing reaction paths and evaluating transition state theory (TST) rate constants for multidimensional, multistate systems. The reaction path is represented as a tethered, freely jointed chain of states with configuration specified by minimization of a function that is derived from the differential description of the path. The method is general and applicable to systems of arbitrary dimension and does not require a priori knowledge of the first-order saddle point, or the topology of the states. Also presented is a novel procedure for numerical determination of the TST rate constant. The procedure is based on Monte Carlo importance sampling using a tethered chain with links modeled as harmonic springs. The beads of the chain and the points at which links pierce the dividing surface separating states serve as biased sampling points for Monte Carlo numerical integration. The methods presented here are tested using the Muller potential surface. The application to problems involving transitions between clusters of states, i.e., macrostates, is discussed.


Related Articles

  • Microscopic dynamics of fluids confined between smooth and atomically structured solid surfaces. Somers, Susan A.; Davis, H. Ted // Journal of Chemical Physics;4/1/1992, Vol. 96 Issue 7, p5389 

    Molecular dynamics and the grand canonical Monte Carlo techniques are employed to simulate the structure and dynamics of a fluid in a slit micropore at equilibrium and under Couette flow. Calculated quantities include the fluid’s density profiles, pair correlation functions, diffusion...

  • Molecular dynamics implementation of the Gibbs ensemble calculation. Palmer, Bruce J.; Lo, Chaomei // Journal of Chemical Physics;12/15/1994, Vol. 101 Issue 12, p10899 

    A molecular dynamics version of the Gibbs ensemble calculation is proposed. This calculation is based on an extended Hamiltonian formalism that treats the temperature, volume, and the coupling of a single particle to the rest of the system as continuous dynamical degrees of freedom with their...

  • Computing accurate forces in quantum Monte Carlo using Pulay’s corrections and energy minimization. Casalegno, Mosé; Mella, Massimo; Rappe, Andrew M. // Journal of Chemical Physics;4/22/2003, Vol. 118 Issue 16, p7193 

    In order to overcome the difficulty of optimizing molecular geometry using quantum Monte Carlo methods, we introduce various approximations to the exact force expectation value. We follow Pulay's suggestion [Mol. Phys. 17, 153 (1969)] to correct the Hellmann-Feynman estimator by introducing the...

  • Statistical inelastic cross-section model for the Monte Carlo simulation of molecules with discrete internal energy. Koura, Katsuhisa // Physics of Fluids A;Aug92, Vol. 4 Issue 8, p1782 

    The statistical inelastic cross-section (SICS) model based on the statistical uncorrelation assumption is derived using the microscopic reversibility relation for the Monte Carlo simulation of molecules with discrete internal energy. The SICS model is specified for rotationally inelastic...

  • Calculation of the chemical potential of chain molecules using the staged particle deletion scheme. Boulougouris, Georgios C.; Economou, Ioannis G.; Theodorou, Doros N. // Journal of Chemical Physics;11/1/2001, Vol. 115 Issue 17, p8231 

    A formulation is presented for the calculation of the chemical potential of chain molecules from molecular simulation based on the staged deletion of a test molecule. This formulation is an extension of a formulation presented recently [Boulougouris et al., Mol. Phys. 96, 905 (1999)] for the...

  • Constant pressure hybrid Molecular Dynamics–Monte Carlo simulations. Faller, Roland; de Pablo, Juan J. // Journal of Chemical Physics;1/1/2002, Vol. 116 Issue 1, p55 

    New hybrid Molecular Dynamics-Monte Carlo methods are proposed to increase the efficiency of constant-pressure simulations. Two variations of the isobaric Molecular Dynamics component of the algorithms are considered. In the first, we use the extended-ensemble method of Andersen [H. C. Andersen,...

  • Detailed balance method for chemical potential determination in Monte Carlo and molecular dynamics simulations. Fay, Patrick J.; Ray, John R.; Wolf, Ralph J. // Journal of Chemical Physics;2/1/1994, Vol. 100 Issue 3, p2154 

    We present a new, nondestructive, method for determining chemical potentials in Monte Carlo and molecular dynamics simulations. The method estimates a value for the chemical potential such that one has a balance between fictitious successful creation and destruction trials in which the Monte...

  • Theory and simulation of the swelling of polymer gels. Kenkare, N. R.; Hall, C. K.; Khan, S. A. // Journal of Chemical Physics;7/1/2000, Vol. 113 Issue 1, p404 

    A combined discontinuous molecular dynamics and Monte Carlo simulation technique is used to study the swelling of athermal, continuous-space, near-perfect, trifunctional polymer networks containing hard chains of lengths 20 and 35 immersed in an athermal hard-sphere solvent. The swelling...

  • Puddle-skimming: An efficient sampling of multidimensional configuration space. Rahman, Jay A.; Tully, John C. // Journal of Chemical Physics;5/22/2002, Vol. 116 Issue 20, p8750 

    We examine the effectiveness of a simple method for surmounting energy barriers and enhancing the exploration of configuration space in Monte Carlo (MC) and molecular dynamics (MD) simulations. Proposed previously for treating surface diffusion [M. M. Steiner, P.-A. Genilloud, and J. W. Wilkins,...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics