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Issue 14, 2015
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Solvent response to fluorine-atom reaction dynamics in liquid acetonitrile

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Abstract

Time-resolved infra-red (IR) absorption spectroscopy is used to follow the production of HF from the reaction of fluorine atoms in liquid acetonitrile (CH3CN). Photolysis of dissolved XeF2 using ∼50 fs duration, 267 nm laser pulses generates F atoms and XeF on prompt (sub-ps) timescales, as verified by broadband transient electronic absorption spectroscopy. The fundamental vibrational band of HF in solution spans more than 400 cm−1 around the band centre at 3300 cm−1, and analysis of portions of the time-resolved spectra reveals time constants for the rise in HF absorption that become longer to lower wavenumber. The time constants for growth of 40 cm−1 wide portions of the IR spectra centred at 3420, 3320 and 3240 cm−1 are, respectively, 3.04 ± 0.26, 5.48 ± 0.24 and 7.47 ± 0.74 ps (1 SD uncertainties). The shift to lower wavenumber with time that causes these changes to the time constants is attributed to evolution of the micro-solvation environment of HF following the chemical reaction. The initial growth of the high-wavenumber portion of the band may contain a contribution from relaxation of initially vibrationally excited HF, for which a time constant of 2.4 ± 0.2 ps is deduced from IR pump and probe spectroscopy of a dilute HF solution in acetonitrile.

Graphical abstract: Solvent response to fluorine-atom reaction dynamics in liquid acetonitrile

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Article information


Submitted
06 Feb 2015
Accepted
05 Mar 2015
First published
05 Mar 2015

This article is Open Access

Phys. Chem. Chem. Phys., 2015,17, 9465-9470
Article type
Paper
Author version available

Solvent response to fluorine-atom reaction dynamics in liquid acetonitrile

G. T. Dunning, D. Murdock, G. M. Greetham, I. P. Clark and A. J. Orr-Ewing, Phys. Chem. Chem. Phys., 2015, 17, 9465
DOI: 10.1039/C5CP00774G

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