Revealing Long-range Substituent Effects In The Laser-induced Fluorescence And Dispersed Fluorescence Spectra Of Jet-cooled Ch_xf_3−xch₂o (x = 1, 2, 3) Radicals

Liu, Jinjun

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https://hdl.handle.net/2142/111591 Copy

Description

Title

Revealing Long-range Substituent Effects In The Laser-induced Fluorescence And Dispersed Fluorescence Spectra Of Jet-cooled Ch_xf_3−xch₂o (x = 1, 2, 3) Radicals

Author(s)

Liu, Jinjun

Contributor(s)

• Tarczay, Gyorgy
• Hegedus, Kristof
• Telfah, Hamzeh
• Reza, Md Asmaul
• Bazso, Gabor
• Koncz, Benedek

Issue Date

2021-06-24

Keyword(s)

Atmospheric science

Abstract

The \~{B} - \~{X} laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of the atmospherically important $\beta$-monofluoro ethoxy (MFEO), $\beta$,$\beta$-difluoro ethoxy (DFEO), and $\beta$,$\beta$,$\beta$-trifluoro ethoxy (TFEO) radicals were recorded with vibronic resolution under jet-cooled conditions. To simulate the spectra, Franck-Condon factors were obtained from quantum chemical computations carried out at the CAM-B3LYP/6-311++G(d,p) level of theory. The simulations reproduce well both the LIF and DF spectra. Both conformers (G and T) of MFEO and one (G) of the two conformers of DFEO contribute to the LIF spectrum. A comparison between the experimental and calculated spectra confirms the expected long-range field effects of the CH$_{X}$F$_{3-X}$ group on electronic transition energies and bond strengths, especially in the excited electronic (\~{B}) state. Although TFEO has only one conformer, its LIF spectrum is highly congested, which is attributed to the interaction between CO stretch and the -CF$_{3}$ internal rotation.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

Permalink

http://hdl.handle.net/2142/111591

DOI

10.15278/isms.2021.RE08

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