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Title: Hybrid two-chain simulation and integral equation theory:


Abstract not provided.

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Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
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DOE Contract Number:
Resource Type:
Country of Publication:
United States

Citation Formats

Li, Huimin, Wu, David T., Curro, John Gillette., and McCoy, John Dwane. Hybrid two-chain simulation and integral equation theory:. United States: N. p., 2006. Web.
Li, Huimin, Wu, David T., Curro, John Gillette., & McCoy, John Dwane. Hybrid two-chain simulation and integral equation theory:. United States.
Li, Huimin, Wu, David T., Curro, John Gillette., and McCoy, John Dwane. Wed . "Hybrid two-chain simulation and integral equation theory:". United States. doi:.
title = {Hybrid two-chain simulation and integral equation theory:},
author = {Li, Huimin and Wu, David T. and Curro, John Gillette. and McCoy, John Dwane},
abstractNote = {Abstract not provided.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Feb 01 00:00:00 EST 2006},
month = {Wed Feb 01 00:00:00 EST 2006}

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  • We present results from a hybrid simulation and integral equation approach to the calculation of polymer melt properties. The simulation consists of explicit Monte Carlo (MC) sampling of two polymer molecules, where the effect of the surrounding chains is accounted for by an HNC solvation potential. The solvation potential is determined from the Polymer Reference Interaction Site Model (PRISM) as a functional of the pair correlation function from simulation. This hybrid two-chain MC-PRISM approach was carried out on liquids of polyethylene chains of 24 and 66 CH{sub 2} units. The results are compared with MD simulation and self-consistent PRISM-PY theorymore » under the same conditions, revealing that the two-chain calculation is close to MD, and able to overcome the defects of the PRISM-PY closure and predict more accurate structures of the liquid at both short and long range. The direct correlation function, for instance, has a tail at longer range which is consistent with MD simulation and avoids the short-range assumptions in PRISM-PY theory. As a result, the self-consistent two-chain MC-PRISM calculation predicts an isothermal compressibility closer to the MD results.« less
  • The correlation functions of homonuclear hard-sphere chain fluids are studied using the Wertheim integral equation theory for associating fluids and the Monte Carlo simulation method. The molecular model used in the simulations is the freely jointed hard-sphere chain with spheres that are tangentially connected. In the Wertheim theory, such a chain molecule is described by sticky hard spheres with two independent attraction sites on the surface of each sphere. The OZ-like equation for this associating fluid is analytically solved using the polymer-PY closure and by imposing a single bonding condition. By equating the mean chain length of this associating hardmore » sphere fluid to the fixed length of the hard-sphere chains used in simulation, we find that the correlation functions for the chain fluids are accurately predicted. From the Wertheim theory we also obtain predictions for the overall correlation functions that include intramolecular correlations. In addition, the results for the average intermolecular correlation functions from the Wertheim theory and from the Chiew theory are compared with simulation results, and the differences between these theories are discussed.« less
  • We have extended the Wertheim integral equation theory to mixtures of hard spheres with two attraction sites in order to model homonuclear hard-sphere chain fluids, and then solved these equations with the polymer-Percus--Yevick closure and the ideal chain approximation to obtain the average intermolecular and overall radial distribution functions. We obtain explicit expressions for the contact values of these distribution functions and a set of one-dimensional integral equations from which the distribution functions can be calculated without iteration or numerical Fourier transformation. We compare the resulting predictions for the distribution functions with Monte Carlo simulation results we report here formore » five selected binary mixtures. It is found that the accuracy of the prediction of the structure is the best for dimer mixtures and declines with increasing chain length and chain-length asymmetry. For the equation of state, we have extended the dimer version of the thermodynamic perturbation theory to the hard-sphere chain mixture by introducing the dimer mixture as an intermediate reference system. The Helmholtz free energy of chain fluids is then expressed in terms of the free energy of the hard-sphere mixture and the contact values of the correlation functions of monomer and dimer mixtures. We compared with the simulation results, the resulting equation of state is found to be the most accurate among existing theories with a relative average error of 1.79% for 4-mer/8-mer mixtures, which is the worst case studied in this work. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.« less
  • It is demonstrated that Chandler{endash}Silbey{endash}Ladanyi integral equation theory for the site{endash}site molecular fluids is the limiting case of complete association of more general two-density integral equation theory for associating fluids developed by Wertheim. The analysis is presented for a site{endash}site molecular system with any number and geometrical arrangement of the sites in the molecule and arbitrary type of the site{endash}site pair interaction. {copyright} {ital 1996 American Institute of Physics.}
  • In this study, we reported the development of a new quantum mechanics/molecular mechanics (QM/MM)-type framework to describe chemical processes in solution by combining standard molecular-orbital calculations with a three-dimensional formalism of integral equation theory for molecular liquids (multi-center molecular Ornstein–Zernike (MC-MOZ) method). The theoretical procedure is very similar to the 3D-reference interaction site model self-consistent field (RISM-SCF) approach. Since the MC-MOZ method is highly parallelized for computation, the present approach has the potential to be one of the most efficient procedures to treat chemical processes in solution. Benchmark tests to check the validity of this approach were performed for twomore » solute (solute water and formaldehyde) systems and a simple S{sub N}2 reaction (Cl{sup −} + CH{sub 3}Cl → ClCH{sub 3} + Cl{sup −}) in aqueous solution. The results for solute molecular properties and solvation structures obtained by the present approach were in reasonable agreement with those obtained by other hybrid frameworks and experiments. In particular, the results of the proposed approach are in excellent agreements with those of 3D-RISM-SCF.« less