Carbon tunneling from a single quantum state

被引：162

作者：

Zuev, PS

Sheridan, RS ^{[1
]}

Albu, TV

Truhlar, DG

Hrovat, DA

Borden, WT

机构：

[1] Univ Nevada, Dept Chem 216, Reno, NV 89557 USA

[2] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

[3] Univ Minnesota, Inst Supercomp, Minneapolis, MN 55455 USA

[4] Univ Washington, Dept Chem, Seattle, WA 98195 USA

来源：

SCIENCE | 2003年 / 299卷 / 5608期

关键词：

D O I：

10.1126/science.1079294

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

We observed ring expansion of 1-methylcyclobutylfluorocarbene at 8 kelvin, a reaction that involves carbon tunneling. The measured rate constants were 4.0x10(-6) per second in nitrogen and 4x10(-5) per second in argon. Calculations indicated that at this temperature the reaction proceeds from a single quantum state of the reactant so that the computed rate constant has achieved a temperature-independent limit. According to calculations, the tunneling contribution to the rate is 152 orders of magnitude greater than the contribution from passage over the barrier. We discuss environmental effects of the solid-state inert-gas matrix on the reaction rate.

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页码：867 / 870

页数：4

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