THE QUANTUM DYNAMICS OF HYDROGEN AND DEUTERIUM ON THE PD(111) SURFACE - A PATH-INTEGRAL TRANSITION-STATE THEORY STUDY

被引:49
作者
RICK, SW
LYNCH, DL
DOLL, JD
机构
[1] BROWN UNIV,DEPT CHEM,PROVIDENCE,RI 02912
[2] THINKING MACHINES CORP,CAMBRIDGE,MA 02142
关键词
D O I
10.1063/1.465645
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 surface diffusion constant for hydrogen and deuterium on the palladium (111) surface is calculated using quantum mechanical transition state theory. The rate constants for diffusion into the subsurface layer are also calculated. Quantum effects are seen to be most important for the surface/subsurface transition and cause an inverse isotope effect in which the rate for deuterium is greater than the rate for hydrogen. The results of ground and excited state wave function calculations show localized hydrogenic states, despite large zero point energies, and that the preferred binding site can vary with isotope between surface and subsurface sites. In addition, estimates of the tunneling rate between the surface and subsurface are in qualitative agreement with the low temperature transition state results.
引用
收藏
页码:8183 / 8193
页数:11
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