Infrared Spectra of the 1-Pyridinium (C5H5NH+) Cation and Pyridinyl (C5H5NH and 4-C5H6N) Radicals Isolated in Solid para
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- 作者：Barbara Golec ; Prasanta Das ; Mohammed Bahou ; Yuan-Pern Lee
- 刊名：Journal of Physical Chemistry A
- 出版年：2013
- 出版时间：December 19, 2013
- 年：2013
- 卷：117
- 期：50
- 页码：13680-13690
- 全文大小：621K
- 年卷期：v.117,no.50(December 19, 2013)
- ISSN：1520-5215
文摘
Protonated pyridine and its neutral counterparts (C5H6N) are important intermediates in organic and biological reactions and in the atmosphere. We have recorded the IR absorption spectra of the 1-pyridinium (C5H5NH+) cation, 1-pyridinyl (C5H5NH), and 4-pyridinyl (4-C5H6N) produced on electron bombardment during matrix deposition of a mixture of pyridine (C5H5N) and p-H2 at 3.2 K; all spectra were previously unreported. The IR features of C5H5NH+ diminished in intensity after the matrix was maintained in darkness for 15 h, whereas those of C5H5NH and 4-C5H6N radicals increased. Irradiation of this matrix with light at 365 nm diminished lines of C5H5NH+ and C5H5NH but enhanced lines of 4-C5H6N slightly, whereas irradiation at 405 nm diminished lines of 4-C5H6N significantly. Observed wavenumbers and relative intensities of these species agree satisfactorily with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3LYP/6-31++G(d,p) method. Assignments of C5H5NH and 4-C5H6N radicals were further supported by the observation of similar spectra when a Cl2/C5H5N/p-H2 matrix was irradiated first at 365 nm and then with IR light to generate H atoms to induce the H + C5H5N reaction.