A BORN-OPPENHEIMER APPROXIMATION FOR PATH-INTEGRALS WITH AN APPLICATION TO ELECTRON SOLVATION IN POLARIZABLE FLUIDS

被引:69
作者
CAO, J
BERNE, BJ
机构
[1] Department of Chemistry, Columbia University, New York
关键词
D O I
10.1063/1.465198
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The Born-Oppenheimer approximation is introduced into the path integral expression for the canonical partition function. It is difficult to apply this to simulations. We devise a new adiabatic expression which we call the free energy Born-Oppenheimer approximation which is much easier to simulate. It is shown that this approximation deviates from the exact path-integral expression by no more than does the standard Born-Oppenheimer approximation and we apply it to the problem of an excess electron dissolved in a polarizable fluid.
引用
收藏
页码:2902 / 2916
页数:15
相关论文
共 31 条
[1]  
[Anonymous], 2013, THEORY SIMPLE LIQUID
[2]  
BARKER JA, 1984, RARE GAS SOLIDS
[3]  
BERNE BJ, 1986, ANNU REV PHYS CHEM, V37, P401
[4]   MANY-BODY DISPERSION FORCES OF POLARIZABLE CLUSTERS AND LIQUIDS [J].
CAO, J ;
BERNE, BJ .
JOURNAL OF CHEMICAL PHYSICS, 1992, 97 (11) :8628-8636
[5]   LOW-TEMPERATURE VARIATIONAL APPROXIMATION FOR THE FEYNMAN QUANTUM PROPAGATOR AND ITS APPLICATION TO THE SIMULATION OF QUANTUM-SYSTEMS [J].
CAO, JS ;
BERNE, BJ .
JOURNAL OF CHEMICAL PHYSICS, 1990, 92 (12) :7531-7539
[6]   EXCESS ELECTRONS IN SIMPLE FLUIDS .1. GENERAL EQUILIBRIUM-THEORY FOR CLASSICAL HARD-SPHERE SOLVENTS [J].
CHANDLER, D ;
SINGH, Y ;
RICHARDSON, DM .
JOURNAL OF CHEMICAL PHYSICS, 1984, 81 (04) :1975-1982
[7]   ELECTRONIC STATES OF A TOPOLOGICALLY DISORDERED SYSTEM - EXACT SOLUTION OF THE MEAN SPHERICAL MODEL FOR LIQUIDS [J].
CHANDLER, D ;
SCHWEIZER, KS ;
WOLYNES, PG .
PHYSICAL REVIEW LETTERS, 1982, 49 (15) :1100-1103
[8]   ELECTROSTATIC INTERACTIONS IN PERIODIC COULOMB AND DIPOLAR SYSTEMS [J].
CICHOCKI, B ;
FELDERHOF, BU ;
HINSEN, K .
PHYSICAL REVIEW A, 1989, 39 (10) :5350-5358
[9]   PARTIAL AVERAGING APPROACH TO FOURIER COEFFICIENT PATH INTEGRATION [J].
COALSON, RD ;
FREEMAN, DL ;
DOLL, JD .
JOURNAL OF CHEMICAL PHYSICS, 1986, 85 (08) :4567-4583
[10]   PATH INTEGRAL MONTE-CARLO STUDIES OF THE BEHAVIOR OF EXCESS ELECTRONS IN SIMPLE FLUIDS [J].
COKER, DF ;
BERNE, BJ ;
THIRUMALAI, D .
JOURNAL OF CHEMICAL PHYSICS, 1987, 86 (10) :5689-5702