Comparative Study of Surface Cycloadditions of Ethylene and 2-Butene on the Si(100)-2 × 1 Surface

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2005-02-01
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Lee, Hee
Choi, Cheol
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Ames National Laboratory

Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.

For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.

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Chemistry

The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).

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The Department of Chemistry was founded in 1880.

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1880-present

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Multireference wave functions were used to study the ethylene and 2-butene surface reactions on Si(100) in their lowest energy singlet states. In addition to the diradical pathway, a π-complex pathway on the ethylene surface was found. The net barrier for the latter process is 4.5 kcal/mol higher than that for the former, making the π-complex pathway kinetically less accessible. Therefore, although there is a competition between the two initial channels, the diradical path is slightly favored, and rotational isomerization is possible. However, since the initial potential energy surfaces of the two channels are different, depending on experimental conditions, the branching ratio between the two channels may change. Consequently, the combined effects that would favor one channel over the other may not derive directly from the initial reaction barrier. This provides an explanation of the experimental controversy. As a result, the final distributions of surface products may depend on the experimental kinetic environment, especially when the population change due to the rotational isomerization is expected to be very small. A significantly different reaction channel is found in the 2-butene surface reaction on Si(100), in which a methyl hydrogen easily transfers to the surface yielding a new type of surface product other than the expected [2 + 2] cycloaddition product, with a comparatively small activation barrier. Consequently, the overall surface reactions of ethylene and 2-butene may be quite different. Therefore, direct comparisons between ethylene and 2-butene experimental results would be very useful.

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Reprinted (adapted) with permission from Journal of Physical Chemistry B 109 (2005): 5067, doi:10.1021/jp0501345. Copyright 2005 American Chemical Society.

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Sat Jan 01 00:00:00 UTC 2005
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