Diffusivity, excess entropy, and the potential-energy landscape of monatomic liquids.


The connection between thermodynamic, transport, and potential-energy landscape features is studied for liquids with Lennard-Jones-type pair interactions using both microcanonical molecular-dynamics and isothermal-isobaric ensemble Monte Carlo simulations. Instantaneous normal-mode and saddle-point analyses of two variants of the monatomic Lennard-Jones liquid have been performed. The diffusivity is shown to depend linearly on several key properties of instantaneous and saddle configurations-the energy, the fraction of negative curvature directions, and the mean, maximum, and minimum eigenvalues of the Hessian. Since the Dzugutov scaling relationship also holds for such systems [Nature (London) 381, 137 (1996)], the exponential of the excess entropy, within the two-particle approximation, displays the same linear dependence on energy landscape properties as the diffusivity.

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@article{Chakraborty2006DiffusivityEE, title={Diffusivity, excess entropy, and the potential-energy landscape of monatomic liquids.}, author={Somendra Nath Chakraborty and Charusita Chakravarty}, journal={The Journal of chemical physics}, year={2006}, volume={124 1}, pages={14507} }