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Laser-Induced Fluorescence and Dispersed Fluorescence Spectroscopy of Jet-Cooled Isopentoxy Radicals

DOI:10.1021/acs.jpca.9b07307 期刊:The Journal of Physical Chemistry A 出版年份:2019 更新时间:2025-09-11 14:15:04
摘要: The B?-X? laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of jet-cooled isopentoxy radicals have been obtained. The LIF spectrum of isopentoxy lacks strong transitions to the CO-stretch levels that are typical for alkoxy radicals. Instead, it contains two low-frequency vibrational progressions due to large-amplitude motions of the GG’ and GG conformers involving torsion of the C1C2C3H dihedral angle. Other vibronic bands observed in the LIF spectrum are attributed to the TG conformer. Molecular carriers of the vibronic transitions in the LIF spectrum are identified by comparing the experimentally obtained spectrum and the simulated one. DF spectra of the GG and TG conformers are dominated by strong vibrational progressions of the CO-stretch mode when the origin or the CO-stretch band is pumped. When non-CO-stretch bands are pumped, the DF spectra are dominated by combination bands of the CO-stretch and the pumped mode. ?-X? separations of the GG, and TG conformers were also determined from the DF spectra.
作者: Md. Asmaul Reza,Anam C Paul,Neil James Reilly,Jinjun Liu
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Investigating the B?-X? laser-induced fluorescence and dispersed fluorescence spectra of jet-cooled isopentoxy radicals to understand their molecular structure and properties.

The study successfully observed B?-X? LIF and DF spectra of jet-cooled isopentoxy radicals, identifying three lowest-energy conformers as spectral carriers. The absence of strong transitions to the CO-stretch levels is attributed to low-barriers for β C-C fission or predissociation in the B? state. DF spectra of the GG and TG conformers are dominated by strong vibrational progressions of the CO-stretch mode or its combination with other vibrational modes due to Duschinsky mixing. The ?-X? separations of the GG and TG conformers have been determined to be 409 and 263 cm?1, respectively.

The absence of strong transitions to the CO-stretch levels in the LIF spectrum is attributed to low-barriers for β C-C fission or predissociation in the B? state. The broadening of the DF transitions may be attributed to both the complicated vibronic structure and the low isomerization barriers between conformers.

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