Platinum monofluoride (PtF) and platinum monochloride (PtCl) were detected in the gas phase using a source-modulated microwave spectrometer. The PtF and PtCl radicals were generated in a free space cell using the sputtering reaction from a platinum sheet placed on the inner surface of a stainless steel cathode through a dc glow discharge plasma of CF(4) and Cl(2), respectively, diluted with Ar. Rotational transitions were measured in the region between 150 and 313 GHz.
View Article and Find Full Text PDFThe rotational spectra of NiCO and PdCO in the ground and ν(2) excited vibrational states were observed by employing a source-modulated microwave spectrometer. The NiCO and PdCO molecules were generated in a free space cell by the sputtering reaction of nickel and palladium sheets, respectively, lining the inner surface of a stainless steel cathode with a dc glow plasma of CO and Ar. The molecular constants of NiCO and PdCO were determined by least-squares analysis.
View Article and Find Full Text PDFFourier-transform microwave and millimeter-wave spectra of the iodomethyl radical, CH(2)I, have been observed in the ground vibronic state in the frequency ranges 17-38 GHz and 200-610 GHz, respectively. The pi-electron radical was produced either by iodine abstraction from diiodomethane (CH(2)I(2)) or by hydrogen abstraction from iodomethane (CH(3)I). Seventy-three hyperfine resolved lines owing to the two hydrogen and to the iodine nuclei have been detected in the microwave region, including K(a) = 0 (ortho species) and K(a) = 1 (para species).
View Article and Find Full Text PDFThe chemistry of the group 11 metal cyanide system has been of considerable interest because of the commercial importance of some of the complexes formed in this system. These metal cyanides contain one-dimensional linear -M-CN-M-CN-M- chains in the solid state; however, they have not been observed as free monomeric species. This Article reports the first detection of monomeric AgCN and AuCN in the gas phase by using rotational spectroscopy.
View Article and Find Full Text PDFThe microwave spectrum of the PBr radical in the X (3)Sigma(-) ground electronic state has been observed by a source modulated spectrometer. The PBr radical was generated in a free space cell by an acdc glow discharge in a mixture of PBr(3) with He andor H(2). A spectrum with three spin components for each of the two isotopomers, P(79)Br and P(81)Br, was observed.
View Article and Find Full Text PDFThe rotational spectrum of the NiS radical in the X(3)Sigma(-) state was observed by employing a source-modulation microwave spectrometer. The NiS radical was generated in a free space cell by a dc glow discharge in H(2)S diluted with Ar. The nickel atoms were supplied by the sputtering reaction from a nickel cathode.
View Article and Find Full Text PDFThe millimeter- and submillimeter-wave spectra of the NiI radical in the X (2)Delta(5/2) and A (2)Pi(3/2) states were observed by a source-modulated microwave spectrometer. The NiI radical was generated by a dc glow discharge in the mixture of CH(3)I vapor and Ar gas through the sputtering reaction with a Ni cathode. Observed transition frequencies for each electronic state were independently analyzed using a polynomial energy expression based on Hund's case (c) approximation.
View Article and Find Full Text PDFThe rotational spectra of the CrF and CrCl radicals in the X 6Sigma+ state were observed by employing a Fourier transform microwave spectrometer. The CrF and CrCl radicals were generated by the reaction of laser-ablated Cr with F2 and Cl2, respectively, diluted in Ar. A chromium rod made of chromium powder pasted with epoxy resin was ablated by a Nd:YAG laser.
View Article and Find Full Text PDFThe millimeter- and submillimeter-wave spectra of the NiBr radical in the X (2)Pi(3/2) and A (2)Delta(5/2) states were observed by a source-modulated microwave spectrometer. The NiBr radical was generated in a dc glow discharge through the mixture of Br(2) vapor and Ar gas by the sputtering reaction with a Ni cathode. Observed transition frequencies were independently analyzed for both electronic states using a standard polynomial expression of a Hund's case (c) approximation.
View Article and Find Full Text PDFUnsaturated transition metal carbonyls are important in processes such as organometallic synthesis, homogeneous catalysis, and photochemical decomposition of organometallics. In particular, a metal monocarbonyl offers a zeroth-order model for interpreting the chemisorption of a CO molecule on a metal surface in catalytic activation processes. Quite large numbers of theoretical papers have appeared which predict spectroscopic and structural properties of transition metal carbonyls.
View Article and Find Full Text PDFThe rotational spectra of NiF in the electronic ground (2)Pi state and the lowest electronically excited (2)Sigma state have been observed. The source of nickel atom was sputtering from a nickel electrode or nickel powder placed on a stainless steel electrode. The molecular constants have been determined by a least-squares analysis of the observed transition frequencies.
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