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Journal ArticleDOI

Rough hard sphere theory of the self‐diffusion constant for molecular liquids

David Chandler
- 15 Feb 1975 - 
- Vol. 62, Iss: 4, pp 1358-1363
TLDR
In this paper, a simple theory based on a hard sphere model is used to calculate the self-diffusion constant and the shear viscosity of liquid carbon tetrachloride.
Abstract
A simple theory based on a hard sphere model is used to calculate the self−diffusion constant and the shear viscosity of liquid carbon tetrachloride. The theory accounts for the coupling between translational and rotational motions of molecules. This feature distinguishes the hard sphere theory presented herein with that given recently by other workers. It is shown that the coupling has a large (factor of 2) effect on the diffusion constant, and thus the coupling should not be neglected even for molecules as spherical as carbon tetrachloride. The approximations that are needed to arrive at a hard sphere theory for transport coefficients are discussed in detail. This analysis reveals the strengths and limitations of such a theory.

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Citations
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Journal ArticleDOI

Van der waals picture of liquids, solids, and phase transformations.

TL;DR: The van der Waals picture focuses on the differing roles of the strong short-ranged repulsive intermolecular forces and the longer ranged attractions in determining the structure and dynamics of dense fluids and solids.
Journal ArticleDOI

Vibrational dephasing and frequency shifts of polyatomic molecules in solution

TL;DR: In this paper, a theory for the effects of repulsive and spatially slowly varying attractive forces on the vibrational frequency and dephasing of polyatomic molecular liquids is developed.
Journal ArticleDOI

Trajectory analysis of a kinetic theory for isomerization dynamics in condensed phases

TL;DR: In this article, the authors used an exact microscopic formalism to study the implications of a stochastic model of isomerization dynamics in liquids, where a reaction coordinate moves in a multistable potential and is coupled to a thermal bath via random collisions which occur with a specified average collision frequency.
Journal ArticleDOI

Correlation and prediction of dense fluid transport coefficients. I. n-alkanes

TL;DR: In this article, a method based on considerations of hard-sphere theory is used for simultaneous correlation of the coefficients of viscosity, self-diffusion, and thermal conductivity for then-alcohols, from methanol ton-decanol, in excellent agreement with experiment, over extended temperature and pressure ranges.
Journal ArticleDOI

Tracer diffusion in polyatomic liquids. III

TL;DR: In this paper, the Rough Hard-Sphere theory was used to explain the origins of the energy of activation of diffusion and explain trends not previously understood, in which the diffusion coefficient is the product of a constant rotational factor, Enskog's diffusivity of hard spheres, and a computer generated backscattering coefficient.
References
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Book

Molecular theory of gases and liquids

TL;DR: Molecular theory of gases and liquids as mentioned in this paper, molecular theory of gas and liquids, Molecular theory of liquid and gas, molecular theories of gases, and liquid theory of liquids, مرکز
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Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids

TL;DR: In this paper, the Fourier transform of the pair correlation function is used to calculate the structure factor of a reference system in which the intermolecular forces are entirely repulsive and identical to the repulsive forces in a Lennard-Jones fluid.