Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

11-1999

Journal or Book Title

Journal of the American Chemical Society

Volume

121

Issue

49

First Page

11311

Last Page

11317

DOI

10.1021/ja9914285

Abstract

[2+2] and [4+2] cycloaddition reactions of 1,3-cyclohexadiene on the Si(001) surface were studied. It is shown that not only the [4+2] cycloaddition reaction but also the [2+2] cycloadditions can occur on the Si(001) surface. Surface isomerization reactions connecting [4+2] and [2+2] are very unlikely due to a high energy barrier, implying that the surface reactions are kinetically controlled. Therefore the final surface reaction products are determined during the initial stage of the reactions in contrast with earlier assumptions that the “product distribution is thermodynamically determined”. Our interpretations are consistent with the new experimental results by the Hamers group. According to our CASSCF(6,6) calculations, the nonsymmetric π-complex transition states along the [2+2] cycloaddition mechanism, which has been suggested by many theoretical studies, seem to be an artifact. Nevertheless, the very soft Si dimer buckling motion of the Si(001) surface certainly facilitates the [2+2] reaction.

Comments

Reprinted (adapted) with permission from Journal of the American Chemical Society 121 (1999): 11311, doi:10.1021/ja9914285. Copyright 1999 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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