Absolute entropy and free energy of fluids using the hypothetical scanning method. II. Transition probabilities from canonical Monte Carlo simulations of partial systems

White, Ronald P.; Meirovitch, Hagai
December 2003
Journal of Chemical Physics;12/15/2003, Vol. 119 Issue 23, p12096
Academic Journal
A variant of the hypothetical scanning (HS) method for calculating the absolute entropy and free energy of fluids is developed, as applied to systems of Lennard-Jones atoms (liquid argon). As in the preceding paper (Paper I), a probability P[sub i] approximating the Boltzmann probability of system configuration i, is calculated with a reconstruction procedure based on adding the atoms gradually to an initially empty volume, where they are placed in their positions at i; in this process the volume is divided into cubic cells, which are visited layer-by-layer, line-by-line. At each step a transition probability (TP) is calculated and the product of all the TPs leads to P[sub i]. At step k, k-1 cells have already been treated, where among them N[sub k] are occupied by an atom. A canonical metropolis Monte Carlo (MC) simulation is carried out over a portion of the still unvisited (future) volume thus providing an approximate representation of the N-N[sub k] as yet untreated (future) atoms. The TP of target cell k is determined from the number of visits of future atoms to this cell during the simulation. This MC version of HS, called HSMC, is based on a relatively small number of efficiency parameters; their number does not grow and their values are not changed as the number of the treated future atoms is increased (i.e., as the approximation improves); therefore, implementing HSMC for a relatively large number of future atoms (up to 40 in this study) is straightforward. Indeed, excellent results have been obtained for the free energy and the entropy. © 2003 American Institute of Physics.


Related Articles

  • Absolute entropy and free energy of fluids using the hypothetical scanning method. I. Calculation of transition probabilities from local grand canonical partition functions. Szarecka, Agnieszka; White, Ronald P.; Meirovitch, Hagai // Journal of Chemical Physics;12/15/2003, Vol. 119 Issue 23, p12084 

    The hypothetical scanning (HS) method provides the absolute entropy and free energy from a Boltzmann sample generated by Monte Carlo, molecular dynamics or any other exact simulation procedure. Thus far HS has been applied successfully to magnetic and polymer chain models; in this paper and the...

  • A computational study of 13-atom Ne-Ar cluster heat capacities. Frantz, D. D. // Journal of Chemical Physics;8/8/1997, Vol. 107 Issue 6, p1992 

    Heat capacity curves as functions of temperature were calculated using Monte Carlo methods for the series of Ne13-nArn clusters (0≤n≤13). The clusters were modeled classically using pairwise additive Lennard-Jones potentials. The J-walking (or jump-walking) method was used to...

  • Modeling of ionization of argon in an analytical capacitively coupled radio-frequency glow discharge. Bogaerts, Annemie; Yan, Min // Journal of Applied Physics;9/15/1999, Vol. 86 Issue 6, p2990 

    Presents information on a study which described the use of a hybrid Monte Carlo-fluid model in modeling of electrons, argon ions and fast argon atoms in a capacitively coupled radio frequency glow discharge. Description of the model; Calculation results; Conclusions.

  • Characterization of Ar[sub n]O[sup -] clusters from ab initio and diffusion Monte Carlo calculations. Jakowski, Jacek; Chałasinski, Grzegorz; Gallegos, Joseph; Severson, Mark W.; Szczesniak, M. M. // Journal of Chemical Physics;2/8/2003, Vol. 118 Issue 6, p2748 

    The structure and energetics of the Ar[sub n]O[sup -] clusters for n=1, …,13 have been modeled in the framework of Diffusion Monte Carlo (DMC), using two- and three-body ab initio determined potentials derived previously by Buchachenko et al. [J. Chem. Phys. 112, 5852 (2000)], and Jakowski...

  • The melting of Ar[sub 54]-HF: A canonical parallel tempering simulation. Ghayal, Madhavi Rajan; Curotto, E. // Journal of Chemical Physics;9/8/2000, Vol. 113 Issue 10 

    A classical canonical Monte Carlo computation for Ar[sub 54]-HF between 1 and 50 K is performed. The results demonstrate that the Ar-HF exchange is significantly different in Ar[sub 54]-HF compared to what has been found for Ar[sub 12]-HF. The HF molecule in Ar[sub 54]-HF does not leave the...

  • Grand canonical Monte Carlo simulation of liquid argon. Ruff, Imre; Baranyai, András; Pálinkás, Gábor; Heinzinger, Karl // Journal of Chemical Physics;8/15/1986, Vol. 85 Issue 4, p2169 

    A grand canonical Monte Carlo procedure with fixed values of the chemical potential μ, volume V, and temperature T, is described which is suitable to simulate simple fluids with only a minor increase in computer time in comparison with canonical (N,V,T) simulations and considerably faster...

  • Cavities in the hard-disk crystal: A Monte Carlo simulation study. Sturgeon, Kathy S.; Stillinger, Frank H. // Journal of Chemical Physics;3/15/1992, Vol. 96 Issue 6, p4651 

    The equilibrium pressure in a crystal composed of hard spheres or disks may be determined from the statistical geometry of a single isolated monocavity (one large enough for addition of only one particle). Additional knowledge of the equilibrium concentration of monocavities permits evaluation...

  • On the acceptance probability of replica-exchange Monte Carlo trials. Kofke, David A. // Journal of Chemical Physics;10/15/2002, Vol. 117 Issue 15, p6911 

    An analysis is presented of the average probability of accepting an exchange trial in the parallel-tempering Monte Carlo molecular simulation method. Arguments are given that this quantity should be related to the entropy difference between the phases, and results from simulations of a simple...

  • DSMC calculation of supersonic expansion at a very large pressure ratio. Teshima, Koji; Usami, Masaru // AIP Conference Proceedings;2001, Vol. 585 Issue 1, p737 

    Supersonic expansion of room temperature argon from a sonic orifice at a very large pressure ratio up to 16000 for different stagnation Knudsen numbers, 2×10[SUP-3] and 4×10[SUP-4] is simulated by the DSMC method. In order to calculate a large flowfield different sized cells and a...


Read the Article


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

Try another library?
Sign out of this library

Other Topics