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Thermodynamics from path integrals

Although general functions of momentum are difficult (though not intractable) to evaluate by path integration, certain functions of momentum (and position) can be evaluated straightforwardly. These are thermodynamic quantities such as the energy and pressure, given respectively by

eqnarray149

We shall derive estimators for these two quantities directly from the path integral expression for the partition function. However, let us work with the partition function for an ensemble of 1-particle systems in three dimensions, which is given by

displaymath154

Using the above thermodynamic relation, the energy becomes

eqnarray163

where

displaymath182

is the thermodynamic estimator for the total energy.

Similarly, an estimator for the internal pressure can be derived using tex2html_wrap_inline516 . As we have done in the past for classical systems, the volume dependence can be made explicity by introducing the change of variables:

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In terms of the scaled variables tex2html_wrap_inline518 , the partition function expression reads:

displaymath193

Evaluating the derivative with respect to volume gives the internal pressure:

eqnarray204

where

displaymath244

is the thermodynamic estimator for the pressure. Clearly, both the energy and pressure will be functions of the particle momenta, however, because they are related to the partition function by thermodynamic differentiation, estimators can be derived for them that do not require the off-diagonal elements of the density matrix.



Mark Tuckerman
Mon Mar 29 18:17:04 EST 1999