Density-functional theory

This is a set of theories in statistical mechanics that profit from the fact that the free energy of a system can be cast as a functional of the density. That is, the density (in its usual sense of particles per volume), which is a funtion of the position in inhomogeneous systems, uniquely defines the free energy. By minimizing this free energy one arrives at the true free energy of the system and the equilibrium densify function. The situation parallels the better known electronic density functional theory, in which the energy of a quantum system is shown to be a functional of the electronic density (theorems by Hohenberg, Kohn, Sham, and Mermin.)

Starting from this fact, approximations are usually made in order to approach the true functional of a given system. An important division is made between local and weighed theories. In a local density theory the in which the dependence is local, as exemplified by the (exact) free energy of an ideal system:

$F_{id}=kT\int dr\rho (r)[\log \rho (r)-1-U(r)],$

where $U(r)$ is an external potential. It is an easy exercise to show that Boltzmann's barometric law follows from minimization.

An example of a weighed density theory would be the (also exact) excess free energy for a system of 1D hard rods:

$F_{ex}=-kT\int dz\rho (z)\log[1-t(z)],$

where $t(z)=\int _{z-\sigma }^{z}dy\rho (y)$, precisely an average of the density over the length of the hard rods, $\sigma$. "Excess" means "over ideal", i.e., it is the total $F=F_{id}+F_{ex}$ that is to be minimized.

See also

• Ebner-Saam-Stroud
• Fundamental-measure theory
• Hohenberg-Kohn-Mermin theorems
• Quantum density-functional theory
• Ramakrishnan-Youssouff
• Weighted density approximation
• Tarazona
• Dynamical density-functional theory

Interesting reading

1. Robert Evans "Density Functionals in the Theory of Nonuniform Fluids", in "Fundamentals of Inhomogeneous Fluids" (ed. D. Henderson). Marcel Dekker.
2. Robert G. Parr "Density Functional Theory", Annual Review of Physical Chemistry 34 pp. 631-656 (1983)
3. C. Ebner, H. R. Krishnamurthy and Rahul Pandit "Density-functional theory for classical fluids and solids", Physical Review A 43 pp. 4355 - 4364 (1991)