The free radical HCCN was produced in an Ar matrix via photolysis of its precursor diazoacetonitrile, NNCHCN, with radiation of wavelengths longer than 350 nm. The ir spectra of HCCN and three isotopic modifications (DCCN, HC13CN, and HCC15N) were obtained, and normal coordinate analyses based on two different geometries, bent and linear, were carried out. The results provide a determination of the general valence force field, and favor the linear, allenic configuration H–Ċ=C=Ṅ. The electronic spectrum of HCCN in an argon matrix was also obtained. A tentative assignment of the band system observed in the uv part of the spectrum has been made.
A high-vacuum cell designed for obtaining surface-enhanced Raman scattering (SERS) spectra of thin films on nonmetallic surfaces is described. The cell is shown to improve one's ability to obtain SERS spectra with acceptable S/N ratios and drastically reduced interference from sample alteration and/or bands typically assigned to graphitic carbon. This cell forms the basis of a pragmatic approach to obtaining SERS spectra from interfacial systems that applied surface scientists will likely be faced with in their work. We have applied this new sampling approach to the study of thin films of polystyrene, palmitic acid, and cetyltrimethylammonium bromide deposited on Si surfaces.
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