REACTION DYNAMICS ON BARRIERLESS REACTION SURFACES - A MODEL FOR ISOERGIC GAS-PHASE PROTON-TRANSFER REACTIONS

被引:42
作者
LIM, KF [1 ]
BRAUMAN, JI [1 ]
机构
[1] STANFORD UNIV, DEPT CHEM, STANFORD, CA 94305 USA
关键词
D O I
10.1063/1.460724
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 kinetics of some gas-phase alcohol/alkoxide proton-transfer reactions is slower than predicted by simple Rice-Ramsberger-Kassel-Marcus (RRKM) rate theory modeling on the near-barrierless reaction surfaces. Reaction dynamics can be investigated in isolation from nonequilibrium and/or thermodynamic considerations through the study of a generic isoergic ion-molecule system X- + X - H. Monte Carlo quasiclassical trajectory simulations on barrierless reaction surfaces show that the slow experimental kinetics is consistent with both (i) locking of the external rotations of the reactants and (ii) passage over the (orbital angular momentum) centrifugal barrier being the rate-determining steps in bimolecular association, rather than only the latter process. In addition, there may be non-RRKM product selectivity.
引用
收藏
页码:7164 / 7180
页数:17
相关论文
共 94 条
[1]   VIBRONIC EFFECTS IN HYDROGEN BONDING [J].
ANDERSON, GR ;
LIPPINCO.ER .
JOURNAL OF CHEMICAL PHYSICS, 1971, 55 (08) :4077-&
[2]  
[Anonymous], 1972, UNIMOLECULAR REACTIO
[3]  
[Anonymous], 1955, MOL VIBRATIONS
[4]  
[Anonymous], 1967, ADV CHEM PHYS, DOI 10.1002/9780470140154.ch5
[5]  
[Anonymous], 1979, MONTE CARLO METHODS
[6]  
BAER S, 1990, THESIS STANFORD U
[7]  
BAER S, IN PRESS J AM CHEM S
[8]   HYDROGEN DEUTERIUM-EXCHANGE REACTIONS OF METHOXIDE METHANOL CLUSTERS [J].
BARLOW, SE ;
DANG, TT ;
BIERBAUM, VM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (19) :6832-6838
[9]   THE KINETICS OF CERTAIN IONIC EXCHANGE REACTIONS OF THE 4 METHYL HALIDES IN AQUEOUS SOLUTION [J].
BATHGATE, RH ;
MOELWYNHUGHES, EA .
JOURNAL OF THE CHEMICAL SOCIETY, 1959, (SEP-O) :2642-2648
[10]  
Benson, 1976, THERMOCHEMICAL KINET, V23, P613