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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 6603-6609 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The exact system of equations for the two-particle distribution function of the system of particles with the Coulomb interaction potential is transformed into the set of equations with the first equation describing the purely Coulomb interaction, the second—the short-range interaction, and the third—the mixed interactions. For each of these equations we choose its own approximation of the bridge functional. In the short-range interaction it is the Martynov–Sarkisov approximation, which gives the best results for systems with the Lenard-Johns interaction potential; in the "mixed'' equation it is the hypernetted-chain approximation, which ensures the highest accuracy in systems with the electrostatic potential; the third equation, which does not contain the bridge functional at all, is retained in its original exact form. The system of three approximate equations obtained in this way proves to be more exact than any of the presently known approximations. At the density close to the melt crystallization density and at the corresponding "melting'' temperatures the thermodynamical inconsistency in pressure is calculated to be several percent and the accuracy in determination of the internal energy is still more high (deviations from the Monte Carlo data do not exceed fractions of percent).
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 1942-1947 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Explicit formulas for the excess chemical potential and Helmholtz free energy have been derived in different ways making use of a functional integration technique. The method employed is an extension of the Kirkwood "charging'' procedure and involves a new way of renormalizing cluster series. The formulas require only the correlation functions for the system under investigation. New and old ways of calculating the free energy of a simple fluid are compared and discussed. Numerical results for the various closures are presented for hard and Lennard-Jones sphere fluids. A bridge functional of the first kind has been introduced and some approximations for this have been proposed and tested.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 3445-3451 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: An equation based on the Ornstein–Zernike theory is suggested to describe the asymptotic behavior of the two-particle distribution function. The equation is shown to be the general one. It is possible to study the long-range part of the correlation function for any interparticle interaction potential as well as for any closure of the Ornstein–Zernike equation. Calculations are performed for a hard-sphere particle system for hypernetted chain, Percus–Yevick, and Martynov–Sarkisov approximate integral equations.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 5249-5258 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We propose self-consistent solutions to the Ornstein–Zernike equation where the approximate closure is replaced by a bridge function expansion, whose main advantage is the improvement of correlation functions. Unknown coefficients of this expansion are found from the principle of total thermodynamic consistency. The latter includes not only the conventional pressure–compressibility equation but also the relation between internal energy and pressure. We show that utilizing only the first equation one may face a nonunique partially consistent solution conditioned by noncomplete formulation of the consistency problem. At the same time the suggested set of equations is sufficient to determine a true and unique physical solution regardless of the number of unknown coefficients. In this paper we expand the bridge function in powers of potential of mean force and perform the example of building the approximate self-consistent closure. Moreover, the approach via total thermodynamic consistency introduces the value of residual inconsistency as the internal criterion of accuracy, which is equal to zero only for the exact closure relation and the corresponding solution. This value is found to be in agreement with the deviation of thermodynamic quantities from numeric simulation data. The proposed method is tested on the classical model of a Lennard-Jones fluid in a wide range of temperatures and high densities.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 3961-3969 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A closure for the Ornstein–Zernike equation was proposed on the basis of an analysis of the properties of bridge functionals. The closure allows one to calculate the two-particle distribution function g(r) of the Lennard-Jones fluid with a relative error that does not exceed 1%–2% at all densities and temperatures. At the same time, the thermodynamic parameters of fluid in the same approximation are calculated with larger error. It has been shown that these facts are due to those additional errors that are entered by the formulas establishing the linkage between g(r) and thermodynamic parameters. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 6095-6101 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We propose a statistical approach to the first order phase transitions problem. For this purpose a self-consistent method for the calculation of high-order virial terms together with efficient numeric realization are developed. The method is based on the idea of differential conditions for thermodynamic consistency what makes possible the calculation of up to 30 virial terms. It is shown numerically that the obtained expansion is convergent. In the accordance with the Lee and Yang theorem, the convergency limit of virial series is found to correspond to the condensation curve. The unknown properties of high order virial terms are revealed. We show that near the critical temperature, the remainder of virial series vanishes, with high order virial terms being close to zero and the properties of a fluid being determined by the first 4–5 terms. The results are tested for two model systems; the square well and Lennard-Jones potentials. Our estimates for the phase transition curve are in good agreement with independent numeric simulation data. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and mathematical physics 22 (1975), S. 59-66 
    ISSN: 1573-9333
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics , Physics
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and mathematical physics 22 (1975), S. 184-189 
    ISSN: 1573-9333
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics , Physics
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and mathematical physics 103 (1995), S. 433-443 
    ISSN: 1573-9333
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics , Physics
    Notes: Abstract The BBGKY hierarchy is expanded in a series with respect to the small parameter $$\varepsilon = {\sigma \mathord{\left/ {\vphantom {\sigma \mathcal{L}}} \right. \kern-\nulldelimiterspace} \mathcal{L}}$$ , where σ is the diameter of the particles, and $$\mathcal{L}$$ is a characteristic macroscopic length (for example, the diameter of the system). Since neither σ nor $$\mathcal{L}$$ occurs explicitly in the equations of the hierarchy, a preliminary step consists of separation from the distribution functions $$\mathcal{G}_{(l)} $$ of short-range components that vary over distances of order σ and long-range components that vary over distances of order $$\mathcal{L}$$ . By a transition to dimensionless variables, terms of zeroth and first order in ε in the hierarchy are separated, this making it possible to perform the expansion with respect to ε. It is shown that in the zeroth order in ε the BBGKY hierarchy determines a state of local equilibrium that for any matter density can be described by a Maxwell distribution “with shift.” The higher terms of the series in ε describe the deviations from local equilibrium. At the same time, the long-range correlations that always arise in nonequilibrium systems are described by the balance equations for mass, momentum, and energy, which are also a consequence of the BBGKY hierarchy, whereas the short-range correlations are described by the equations for $$\mathcal{G}_{(l)} $$ obtained from the same hierarchy by expanding $$\mathcal{G}_{(l)} $$ in a series with respect to ε.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Journal of structural chemistry 27 (1986), S. 78-83 
    ISSN: 1573-8779
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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