USE OF AN IMPROVED ION-SOLVENT POTENTIAL-ENERGY FUNCTION TO CALCULATE THE REACTION-RATE AND ALPHA-DEUTERIUM AND MICROSOLVATION KINETIC ISOTOPE EFFECTS FOR THE GAS-PHASE SN2 REACTION OF CL-(H2O) WITH CH3CL

被引:51
作者
ZHAO, XG
LU, DH
LIU, YP
LYNCH, GC
TRUHLAR, DG
机构
[1] UNIV MINNESOTA, DEPT CHEM, CHEM PHYS PROGRAM, MINNEAPOLIS, MN 55455 USA
[2] UNIV MINNESOTA, INST SUPERCOMP, MINNEAPOLIS, MN 55455 USA
关键词
D O I
10.1063/1.463698
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
We present calculations of the rate constants and secondary kinetic isotope effects for gas-phase S(N)2 reaction Cl- (H2O) + CH3Cl based on a new chloride-water potential-energy function that has been specifically converged for heavy-water isotope effects. The results are compared to new calculations employing five chloride-water potential-energy functions that have been developed for simulations of aqueous solutions. In all calculations the ClCH3Cl- solute intramolecular potential is taken from a previous semiglobal fit to ab initio calculations including electron correlation. We also examine two different intramolecular water potentials, and we examine the effect of treating the CH3 internal rotation at the ClCH3Cl- (H2O) transition state as a hindered rotation. Both the CH3/CD3 (alpha-deuterium) and H2O/D2O (microsolvation) kinetic isotope effects are studied.
引用
收藏
页码:6369 / 6383
页数:15
相关论文
共 101 条
[81]   INITIAL-STATE AND TRANSITION-STATE ISOTOPE EFFECTS OF METHYL HALIDES IN LIGHT AND HEAVY WATER [J].
SWAIN, CG ;
THORNTON, ER .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1962, 84 (05) :822-&
[82]   PHYSICAL ORGANIC CHEMISTRY [J].
THORNTON, ER .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 1966, 17 :349-&
[83]  
TOPSOM RD, 1990, PROG PHYS ORG CHEM, V17, P107
[84]  
Truhlar D. G., 1985, THEORY CHEM REACTION, VIV, P65
[85]   POTENTIAL-ENERGY SURFACES FOR POLYATOMIC REACTION DYNAMICS [J].
TRUHLAR, DG ;
STECKLER, R ;
GORDON, MS .
CHEMICAL REVIEWS, 1987, 87 (01) :217-236
[86]  
TRUHLAR DG, 1971, J AM CHEM SOC, V93, P1840
[87]   VARIATIONAL TRANSITION-STATE THEORY [J].
TRUHLAR, DG ;
GARRETT, BC .
ACCOUNTS OF CHEMICAL RESEARCH, 1980, 13 (12) :440-448
[88]   INCORPORATION OF QUANTUM EFFECTS IN GENERALIZED-TRANSITION-STATE THEORY [J].
TRUHLAR, DG ;
ISAACSON, AD ;
SKODJE, RT ;
GARRETT, BC .
JOURNAL OF PHYSICAL CHEMISTRY, 1982, 86 (12) :2252-2261
[89]  
TRUHLAR DG, 1991, J COMPUT CHEM, V12, P2661
[90]  
TRUHLAR DG, 1987, FARADAY DISCUSS, V84, P464