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41.
Koichi Yamada Brenda P. Winnewisser Manfred Winnewisser 《Journal of Molecular Spectroscopy》1975,56(3):449-470
The recent assignment of the vibrational spectrum of the quasilinear molecule HCNO revealed several near coincidences between vibrational energy levels involving the two bending modes, ν4 (skeletal bending mode) and ν5 (HCN-bending mode), and the lowest-lying stretching mode, ν3 (NO stretching mode). By considering the correlation between the energy levels of a linear and a bent molecular model of HCNO, it is seen that resonance interactions which would be of third or higher order in a linear molecule Hamiltonian would be of first or second order in the Hamiltonian of a bent molecule, and thus might be significant in the quasilinear molecule HCNO. In this way we were able to identify the type of observed interaction occurring between three pairs of nearly coincident levels, (00010, 00002), (00020, 00012), and (00100, 00004). Anomalous centrifugal distortion effects had been observed and reported earlier for the pure rotational transitions arising from molecules in the 00010, 00020, and 00002 levels. Rotational transitions arising from molecules in the 00004 and 00100 vibrational states of HCNO and the 00100 state of DCNO are reported here for the first time. For two pairs of levels, (00010, 00002) and (00100, 00004), we could determine the magnitude of the coefficients of the interaction matrix elements from an analysis of the centrifugal distortion effects. 相似文献
42.
Gisbert Depke Walter Klose Helmut Schwarz Wolfgang Blum Wilhelm J. Richter 《Journal of mass spectrometry : JMS》1983,18(12):568-571
Unimolecular hydroxyl (OD˙) loss from regio- and stereo-specifically labelled o-nitrostyrenes 1a, 1c and 1d results in the formation of an ion which upon collisional activation gives identical mass spectra. Suggestions are made which aim at explaining: (i) the loss of stereochemical integrity of the diastereotopic methylene hydrogens in the course of hydroxyl elimination; and (ii) to account for the collision induced losses of CO and HNC from the [M—hydroxyl]+ ion. 相似文献
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The semirigid bender Hamiltonian [Bunker and Landsberg, J. Mol. Spectrosc., 67, 374–385 (1977)] is used to fit the rotation-vibration energy level separations in the fulminic acid (HCNO) molecule. The allowance made in the model for the variation of the CH and CN bond lengths with the HCN bending angle proves to be very important, and as well as achieving a good fit we are able to make a detailed investigation of the shape of the HCN bending potential function.From the results we conclude that the equilibrium structure of HCNO is linear but that excitation of the ν1 or ν2 stretching vibrations gives rise to an effective HCN bending potential function having its minimum at a nonlinear configuration. Even in the ground state the zeropoint vibrational contributions from ν1 and ν2 to the effective HCN bending potential give a small barrier (11.5 cm?1) to linearity, and we determine that the zero-point HCN bending vibrational amplitude is ±34°. 相似文献
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Dr. Tiago Rodrigues Dr. Petra Schneider Prof. Dr. Gisbert Schneider 《Angewandte Chemie (International ed. in English)》2014,53(23):5750-5758
Flow systems have been successfully utilized for a wide variety of applications in chemical research and development, including the miniaturization of (bio)analytical methods and synthetic (bio)organic chemistry. Currently, we are witnessing the growing use of microfluidic technologies for the discovery of new chemical entities. As a consequence, chemical biology and molecular medicine research are being reshaped by this technique. In this Minireview we portray the state‐of‐the‐art, including the most recent advances in the application of microchip reactors as well as the micro‐ and mesoscale coil reactor‐assisted synthesis of bioactive small molecules, and forecast the potential future use of this promising technology. 相似文献
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