STRUCTURE AND DYNAMICS OF WATER AND AQUEOUS-SOLUTIONS - THE ROLE OF FLEXIBILITY

被引:81
作者
SMITH, DE
HAYMET, ADJ
机构
[1] Department of Physical and Theoretical Chemistry, University of Sydney
关键词
D O I
10.1063/1.462297
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 role molecular flexibility plays in the chemistry of bulk water and ionic solutions is evaluated using molecular dynamics simulations. For simplicity the flexible water model used here is the revised central force (CF) model of Stillinger and Rahman [J. Chem. Phys. 68, 666 (1977)]. A companion, rigid central force (RCF) model is invented to provide the most accurate average description of CF water. Discussion of the role of flexibility is divided into effects due to Coulombic and non-Coulombic parts of the potential energy. The Coulombic part provides the connection between flexibility and nuclear polarizability. A variety of thermodynamic and dynamical properties of the two models are compared. These include the static dielectric constant, orientational correlation functions, self-diffusion coefficient, pressure, intermolecular energy, and pair correlation functions. The effect of flexibility is greatest for dielectric properties, but in general it is found to be small. The dielectric constant of CF water is measured to be approximately 77, in good-perhaps fortuitous-agreement with the experimental value. A variety of ionic solution properties, including the free energy and dynamics of ionic association, are reported for model sodium chloride solutions at two concentrations. For these quantities also the effect of water flexibility is found to be small.
引用
收藏
页码:8450 / 8459
页数:10
相关论文
共 70 条
[1]  
Allen M.P., 1987, COMPUTER SIMULATION
[3]   MOLECULAR-DYNAMICS SIMULATION OF DIELECTRIC-PROPERTIES OF WATER [J].
ANDERSON, J ;
ULLO, JJ ;
YIP, S .
JOURNAL OF CHEMICAL PHYSICS, 1987, 87 (03) :1726-1732
[4]   THE ROLE OF LONG RANGED FORCES IN DETERMINING THE STRUCTURE AND PROPERTIES OF LIQUID WATER [J].
ANDREA, TA ;
SWOPE, WC ;
ANDERSEN, HC .
JOURNAL OF CHEMICAL PHYSICS, 1983, 79 (09) :4576-4584
[5]  
[Anonymous], 2001, INTERMOLECULAR FORCE, DOI DOI 10.1007/978-94-015-7658-1_21
[6]   THE ROLE OF MOLECULAR FLEXIBILITY IN SIMULATIONS OF WATER [J].
BARRAT, JL ;
MCDONALD, IR .
MOLECULAR PHYSICS, 1990, 70 (03) :535-539
[7]  
BARTLETT RJ, 1979, J CHEM PHYS, V71, P281, DOI 10.1063/1.438069
[8]   THEORETICAL-STUDY OF ION SOLVATION AT THE WATER LIQUID-VAPOR INTERFACE [J].
BENJAMIN, I .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (05) :3698-3709
[9]   THE MISSING TERM IN EFFECTIVE PAIR POTENTIALS [J].
BERENDSEN, HJC ;
GRIGERA, JR ;
STRAATSMA, TP .
JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (24) :6269-6271
[10]   MOLECULAR-DYNAMICS WITH COUPLING TO AN EXTERNAL BATH [J].
BERENDSEN, HJC ;
POSTMA, JPM ;
VANGUNSTEREN, WF ;
DINOLA, A ;
HAAK, JR .
JOURNAL OF CHEMICAL PHYSICS, 1984, 81 (08) :3684-3690