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Register a new userVirial coefficients expressed by heat kernel coefficients
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In this paper, we generally expressed the virial expansion of ideal quantum gases by the heat kernel coefficients for the corresponding Laplace type operator. As examples, we give the virial coefficients for quantum gases in $d$-dimensional confined space and spheres, respectively. Our results show that, the relative correction from the boundary to the second virial coefficient is independent of the dimension and it always enhances the quantum exchange interaction. In $d$-dimensional spheres, however, the influence of the curvature enhances the quantum exchange interaction in two dimensions, but weakens it in higher dimensions ($d>3$).
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vant Hoff equation relates equilibrium constant $K$ of a chemical reaction to temperature $T$. Though the vant Hoff plot ($ln K$ vs $1/T$) is linear, it is nonlinear for certain chemical reactions. In this work we attribute such observations to virial coefficients.
We study the virial coefficients B_k of hard spheres in D dimensions by means of Monte-Carlo integration. We find that B_5 is positive in all dimensions but that B_6 is negative for all D >= 6. For 7<=k<=17 we compute sets of Ree-Hoover diagrams and find that either for large D or large k the dominant diagrams are loose packed. We use these results to study the radius of convergence and the validity of the many approximations used for the equations of state for hard spheres.
We compute the fourth virial coefficient of a binary nonadditive hard-sphere mixture over a wide range of deviations from diameter additivity and size ratios. Hinging on this knowledge, we build up a $y$ expansion [B. Barboy and W. N. Gelbart, J. Chem. Phys. {bf 71}, 3053 (1979)] in order to trace the fluid-fluid coexistence lines which we then compare with the available Gibbs-ensemble Monte Carlo data and with the estimates obtained through two refined integral-equation theories of the fluid state. We find that in a regime of moderately negative nonadditivity and largely asymmetric diameters, relevant to the modelling of sterically and electrostatically stabilized colloidal mixtures, the fluid-fluid critical point is unstable with respect to crystallization.
We compute the shear and bulk viscosities, as well as the thermal conductivity of an ultrarelativistic fluid obeying the relativistic Boltzmann equation in 2+1 space-time dimensions. The relativistic Boltzmann equation is taken in the single relaxation time approximation, based on two approaches, the first, due to Marle and using the Eckart decomposition, and the second, proposed by Anderson and Witting and using the Landau-Lifshitz decomposition. In both cases, the local equilibrium is given by a Maxwell-Juettner distribution. It is shown that, apart from slightly different numerical prefactors, the two models lead to a different dependence of the transport coefficients on the fluid temperature, quadratic and linear, for the case of Marle and Anderson-Witting, respectively. However, by modifying the Marle model according to the prescriptions given in Ref.[1], it is found that the temperature dependence becomes the same as for the Anderson-Witting model.
Thermal transport coefficients are independent of the specific microscopic expression for the energy density and current from which they can be derived through the Green-Kubo formula. We discuss this independence in terms of a kind of gauge invariance resulting from energy conservation and extensivity, and demonstrate it numerically for a Lennard-Jones fluid, where different forms of the microscopic energy density lead to different time correlation functions for the heat flux, all of them, however, resulting in the same value for the thermal conductivity.
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