Statistical mechanical models with effective potentials: Definitions, applications, and thermodynamic consequences
نویسندگان
چکیده
Realistic interactions that operate in condensed matter systems can exhibit complicated many-particle characteristics. However, it is often useful to seek a more economical description using at most singlet and pair effective interactions that are density dependent, to take advantage of the theoretical and computational simplifications that result. This paper analyzes the statistical mechanical formalism required to describe thermal equilibrium in that kind of approach. Two distinct interpretations are available for the role of density dependence. Either one can be treated with internal consistency, but generally they lead to differing thermodynamic predictions. One regards the density dependence of effective interactions as merely a passive index for the state at which the optimal choice of those effective interactions was determined ~Case I!. The other treats the density as an active variable on the same footing as particle coordinates ~Case II!. Virial pressure and isothermal compressibility expressions in terms of particle distribution functions are displayed for both cases. Under special circumstances it is possible for the two interpretations to yield the same pressure isotherms; the conditions producing this coincidental concordancy have been explored by means of density expansions. © 2002 American Institute of Physics. @DOI: 10.1063/1.1480863#
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تاریخ انتشار 2002