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The diffusion constant

The diffusive flow of particles can be studied by applying a constant force f to a system using the microscopic equations of motion

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which have the conserved energy

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Since the force is applied in the tex2html_wrap_inline845 direction, there will be a net flow of particles in this direction, i.e., a current tex2html_wrap_inline895 . Since this current is a thermodynamic quantity, there is an estimator for it:

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and tex2html_wrap_inline897 . The constant force can be considered as arising from a potential field

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The potential gradient tex2html_wrap_inline899 will give rise to a concentration gradient tex2html_wrap_inline901 which is opposite to the potential gradient and related to it by

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However, Fick's law tells how to relate the particle current tex2html_wrap_inline895 to the concentration gradient

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where D is the diffusion constant. Solving for D gives

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Let us apply the linear response formula again to the above nonequilibrium average. Again, we make the identification:

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Thus,

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In equilibrium, it can be shown that there are no cross correlations between different particles. Consider the initial value of the correlation function. From the virial theorem, we have

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which vanishes for tex2html_wrap_inline909 . In general,

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Thus,

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In equilibrium, tex2html_wrap_inline911 being linear in the velocities (hence momenta). Thus, the diffusion constant is given by, when the limit tex2html_wrap_inline839 is taken,

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However, since no spatial direction is preferred, we could also choose to apply the external force in the y or z directions and average the result over the these three. This would give a diffusion constant

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The quantity

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is known as the velocity autocorrelation function, a quantity we will encounter again in other contexts.



Mark Tuckerman
Thu Apr 13 13:07:24 EDT 2000