Smoluchowski equation with a sink term: Analytical solutions for the rate constant and their numerical test

被引:30
作者
Berezhkovskii, AM
D'yakov, YA
Zitserman, VY
机构
[1] LY Karpov Phys Chem Res Inst, Moscow 103064, Russia
[2] Russian Acad Sci, Inst High Temp, Moscow 127412, Russia
关键词
D O I
10.1063/1.477024
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
Smoluchowski equation with a sink term is widely used as a model of a rate process in a slowly relaxing environment. Two approximate solutions for the rate constant obtained for a steeply growing sink are tested numerically using an exponential sink. Both analytical solutions are in a good agreement with the numerical results over a wide range of the problem parameters (environment relaxation rate). They show how the rate constant Gamma decreases when the viscosity eta of the environment increases. If the dependence is approximated by the fractional power law, Gamma proportional to eta(-alpha), the exponent alpha is always less than unity and depends on eta. It tends to zero for fast relaxation of the environment (small eta) and increases when the relaxation slows down (eta grows). (C) 1998 American Institute of Physics.
引用
收藏
页码:4182 / 4189
页数:8
相关论文
共 39 条
[1]   TRANSIENT KINETICS OF CHEMICAL-REACTIONS WITH BOUNDED DIFFUSION PERPENDICULAR TO THE REACTION COORDINATE - INTRAMOLECULAR PROCESSES WITH SLOW CONFORMATIONAL-CHANGES [J].
AGMON, N ;
HOPFIELD, JJ .
JOURNAL OF CHEMICAL PHYSICS, 1983, 78 (11) :6947-6959
[2]   CO BINDING TO HEME-PROTEINS - A MODEL FOR BARRIER HEIGHT DISTRIBUTIONS AND SLOW CONFORMATIONAL-CHANGES [J].
AGMON, N ;
HOPFIELD, JJ .
JOURNAL OF CHEMICAL PHYSICS, 1983, 79 (04) :2042-2053
[3]  
AGMON N, 1984, J CHEM PHYS, V80, P592, DOI 10.1063/1.447296
[4]   THEORY OF ELECTRONIC RELAXATION IN SOLUTION IN THE ABSENCE OF AN ACTIVATION BARRIER [J].
BAGCHI, B ;
FLEMING, GR ;
OXTOBY, DW .
JOURNAL OF CHEMICAL PHYSICS, 1983, 78 (12) :7375-7385
[5]   POLYEXPONENTIAL KINETICS OF CHEMICAL-REACTIONS IN CONDENSED MEDIA WITHIN THE QUASI-CLASSICAL APPROXIMATION [J].
BASILEVSKY, MV ;
DAVIDOVITCH, GV .
JOURNAL OF CHEMICAL PHYSICS, 1995, 102 (04) :1607-1618
[6]   GENERALIZATION OF THE KRAMERS-LANGER THEORY - DECAY OF THE METASTABLE STATE IN THE CASE OF STRONGLY ANISOTROPIC FRICTION [J].
BEREZHKOVSKII, AM ;
ZITSERMAN, VY .
JOURNAL OF PHYSICS A-MATHEMATICAL AND GENERAL, 1992, 25 (08) :2077-2092
[7]   ACTIVATED RATE-PROCESSES IN A MULTIDIMENSIONAL CASE - A NEW SOLUTION OF THE KRAMERS PROBLEM [J].
BEREZHKOVSKII, AM ;
ZITSERMAN, VY .
PHYSICA A, 1990, 166 (03) :585-621
[8]   Kramers theory of chemical reactions in a slowly adjusting environment [J].
Berezhkovskii, AM ;
Zitserman, VY ;
Sheu, SY ;
Yang, DY ;
Kuo, J ;
Lin, SH .
JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (24) :10539-10554
[9]   Molecular motion through fluctuating bottlenecks [J].
Eizenberg, N ;
Klafter, J .
JOURNAL OF CHEMICAL PHYSICS, 1996, 104 (17) :6796-6806
[10]   MOLECULAR-MOTION UNDER STOCHASTIC GATING [J].
EIZENBERG, N ;
KLAFTER, J .
CHEMICAL PHYSICS LETTERS, 1995, 243 (1-2) :9-14