Stochastic dynamics in near-critical supercritical fluids

被引:19
作者
Drozdov, AN
Tucker, SC [1 ]
机构
[1] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
[2] Inst High Temp, Moscow 127412, Russia
关键词
D O I
10.1021/jp010354s
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
An extension of the generalized Langevin equation (GLE) is introduced in order to model diffusion processes in near-critical fluids. Unlike the standard GLE, this new approach allows a flexible description of the influence of slowly fluctuating local density distributions that occur in a fluid as its liquid-vapor critical point is approached. We find that, given an initial nonequilibrium ensemble, diffusion coefficients differing substantially from the expected bulk value can be observed at intermediate times, that is, at times longer than the velocity relaxation time but shorter than the local environment interconversion time.
引用
收藏
页码:6675 / 6683
页数:9
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