Reactions of methylamines at the Si(100)-2×1 surface

We have investigated the room temperature adsorption of methylamine, dimethylamine and trimethylamine using density functional theory (DFT) and multiple internal reflection Fourier transform infrared (MIR-FTIR) spectroscopy. It was found that the reaction pathways of the amines resemble the precurso...

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Veröffentlicht in:The Journal of chemical physics 2001-06, Vol.114 (22), p.10170-10180
Hauptverfasser: Mui, Collin, Wang, George T., Bent, Stacey F., Musgrave, Charles B.
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container_issue 22
container_start_page 10170
container_title The Journal of chemical physics
container_volume 114
creator Mui, Collin
Wang, George T.
Bent, Stacey F.
Musgrave, Charles B.
description We have investigated the room temperature adsorption of methylamine, dimethylamine and trimethylamine using density functional theory (DFT) and multiple internal reflection Fourier transform infrared (MIR-FTIR) spectroscopy. It was found that the reaction pathways of the amines resemble the precursor-mediated dissociative chemisorption of ammonia. Our calculations showed that although dissociation involving N–C bond cleavage is thermodynamically more favorable than the N–H dissociation pathway, the activation barrier for N–CH3 dissociation is significantly higher than that for N–H dissociation. This leads to selective cleavage of N–H bonds in the surface reactions of methylamine and dimethylamine, while trapping trimethylamine in its molecularly chemisorbed state through the formation of a Si–N dative bond. We also identified the products of the reactions of the amines on the Si(100)-2×1 surface by surface IR studies, confirming the theoretical predictions. The selectivity observed in the surface chemistry of simple model amines is briefly discussed in the context of organic chemistry at semiconductor surfaces.
doi_str_mv 10.1063/1.1370056
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title Reactions of methylamines at the Si(100)-2×1 surface
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