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The value of different experimental observables : a transient absorption study of the ultraviolet excitation dynamics operating in nitrobenzene
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Crane, Stuart W., Garrow, Malcolm, Lane, Paul D., Robertson, Kate, Waugh, Alex, Woolley, Jack M., Stavros, Vasilios G., Paterson, Martin J., Greaves, Stuart J. and Townsend, Dave (2023) The value of different experimental observables : a transient absorption study of the ultraviolet excitation dynamics operating in nitrobenzene. The Journal of Physical Chemistry A, 127 (31). pp. 6425-6436. doi:10.1021/acs.jpca.3c02654 ISSN 1089-5639.
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Official URL: http://dx.doi.org/10.1021/acs.jpca.3c02654
Abstract
Excess energy redistribution dynamics operating in nitrobenzene under hexane and isopropanol solvation were investigated using ultrafast transient absorption spectroscopy (TAS) with a 267 nm pump and a 340–750 nm white light continuum probe. The use of a nonpolar hexane solvent provides a proxy to the gas-phase environment, and the findings are directly compared with a recent time-resolved photoelectron imaging (TRPEI) study on nitrobenzene using the same excitation wavelength [L. Saalbach et al., J. Phys. Chem. A 2021, 125, 7174–7184]. Of note is the observation of a 1/e lifetime of 3.5–6.7 ps in the TAS data that was absent in the TRPEI measurements. This is interpreted as a dynamical signature of the T2 state in nitrobenzene─analogous to observations in the related nitronaphthalene system, and additionally supported by previous quantum chemistry calculations. The discrepancy between the TAS and TRPEI measurements is discussed, with the overall findings providing an example of how different spectroscopic techniques can exhibit varying sensitivity to specific steps along the overall reaction coordinate connecting reactants to photoproducts.
Item Type: | Journal Article | |||||||||||||||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Physics | |||||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Nitrobenzene, Ultraviolet spectroscopy, Flash photolysis | |||||||||||||||||||||
Journal or Publication Title: | The Journal of Physical Chemistry A | |||||||||||||||||||||
Publisher: | American Chemical Society | |||||||||||||||||||||
ISSN: | 1089-5639 | |||||||||||||||||||||
Official Date: | 10 August 2023 | |||||||||||||||||||||
Dates: |
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Volume: | 127 | |||||||||||||||||||||
Number: | 31 | |||||||||||||||||||||
Page Range: | pp. 6425-6436 | |||||||||||||||||||||
DOI: | 10.1021/acs.jpca.3c02654 | |||||||||||||||||||||
Status: | Peer Reviewed | |||||||||||||||||||||
Publication Status: | Published | |||||||||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||||||||
Date of first compliant deposit: | 29 August 2023 | |||||||||||||||||||||
Date of first compliant Open Access: | 31 August 2023 | |||||||||||||||||||||
RIOXX Funder/Project Grant: |
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