The explicit density functional and its connection with entropy maximization

被引:19
作者
Attard, P [1 ]
机构
[1] Univ S Australia, Ian Wark Res Inst, Mawson Lakes, SA 5095, Australia
关键词
density functional theory; cluster diagrams; maximum entropy;
D O I
10.1023/A:1018668502023
中图分类号
O4 [物理学];
学科分类号
0702 ;
摘要
The intrinsic Helmholtz free energy, commonly used as a basis for density functional theories, is here given explicitly as a cluster diagram expansion with density field points, Also given are explicit variational procedures For determining the chemical potential for a given density, the pair potential For a given pail correlation function, and the pair correlation function ibr a given pair potential. The physical meaning of the density functional is established within the context of a new derivation of statistical mechanics based on entropy th;lt supplies a variational principle for equilibrium by generalizing the thermodynamic potential to nonequlibrium states. This shows that the conventional density functional determines not only the equilibrium density, but also the probability of fluctuations about that density.
引用
收藏
页码:445 / 473
页数:29
相关论文
共 16 条
[1]   THE ELECTRICAL DOUBLE-LAYER IN WALL-WALL HYPERNETTED-CHAIN APPROXIMATION WITH BRIDGE FUNCTIONS [J].
ATTARD, P ;
MIKLAVIC, SJ .
JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (08) :6078-6086
[2]   PAIR-HYPERNETTED-CHAIN CLOSURE FOR 3-BODY POTENTIALS - RESULTS FOR ARGON WITH THE AXILROD-TELLER TRIPLE-DIPOLE POTENTIAL [J].
ATTARD, P .
PHYSICAL REVIEW A, 1992, 45 (06) :3659-3669
[3]   HYPERNETTED-CHAIN CLOSURE WITH BRIDGE DIAGRAMS - ASYMMETRIC HARD-SPHERE MIXTURES [J].
ATTARD, P ;
PATEY, GN .
JOURNAL OF CHEMICAL PHYSICS, 1990, 92 (08) :4970-4982
[4]   THE CHEMICAL-POTENTIAL IN TERMS OF N-PARTICLE DIRECT CORRELATION-FUNCTIONS [J].
ATTARD, P .
JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (03) :2370-2371
[5]   LENNARD-JONES BRIDGE FUNCTIONS AND TRIPLET CORRELATION-FUNCTIONS [J].
ATTARD, P .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (06) :4471-4480
[6]  
ATTARD P, UNPUB
[7]  
Callan H B, 1960, THERMODYNAMICS
[9]   VARIATIONAL FORMULATIONS OF EQUILIBRIUM STATISTICAL MECHANICS [J].
DEDOMINICIS, C .
JOURNAL OF MATHEMATICAL PHYSICS, 1962, 3 (05) :983-+
[10]   NATURE OF THE LIQUID-VAPOR INTERFACE AND OTHER TOPICS IN THE STATISTICAL-MECHANICS OF NONUNIFORM, CLASSICAL FLUIDS [J].
EVANS, R .
ADVANCES IN PHYSICS, 1979, 28 (02) :143-200