Reaction of tert-butyl isocyanate and tert-butyl isothiocyanate at the Ge(100)-2 x 1 Surface

The adsorption of tert-butyl isothiocyanate and tert-butyl isocyanate at the Ge(100) - 2 x 1 surface was probed using multiple internal reflection Fourier transform infrared (FTIR) spectroscopy X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) modeling. Results indicate that there are multiple surface products for each molecule. FUR studies of tert-butyl isothiocyanate reveal adsorption through an S-dative bonded state, while XPS studies further suggest a reactive desorption product which leaves excess sulfur atoms at the surface. Studies of tert-butyl isocyanate indicate that the molecule dissociatively adsorbs at the surface, resulting in tert-butyl and germyl isocyanate groups, as the major pathway, in addition to forming several minor products, including a [2 + 2] cycloaddition product across the C=N bond. OFT was used to simulate vibrational spectra and map the reaction pathways, and confirms that the assigned products are energetically favorable. (C) 2010 Elsevier B.V. All rights reserved.