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New insights into the dissociation dynamics of methylated anilines
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Cole-Filipiak, Neil C. and Stavros, Vasilios G. (2019) New insights into the dissociation dynamics of methylated anilines. Physical Chemistry Chemical Physics, 21 (26). pp. 14394-14406. doi:10.1039/c8cp07061j ISSN 1463-9076.
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Official URL: https://doi.org/10.1039/c8cp07061j
Abstract
Aniline, an important model system for biological chromophores, undergoes ultrafast H-atom loss upon absorption of an ultraviolet photon. By varying the number and position of methyl substituents on both the aromatic ring and amine functional group, we explore the ultrafast production of photofragments as a function of molecular structure. Both N-methyl aniline and 3,5-dimethyl aniline show altered H-atom loss behaviour compared to aniline, while no evidence for CH3 loss was found from either N-methyl aniline or N,N-dimethyl aniline. With the addition of time-resolved photoelectron spectroscopy, the photofragment appearance times are matched to excited state relaxation pathways. Evidence for a sequential excited state relaxation mechanism, potentially involving a valence-to-Rydberg decay mechanism, will be presented. Such a global, bottom-up approach to molecular photochemistry is crucial to understanding the dissociative pathways and excited state decay mechanisms of biomolecule photoprotection in nature.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QC Physics Q Science > QD Chemistry |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
Library of Congress Subject Headings (LCSH): | Aniline, Photoelectron spectroscopy, Photochemistry | ||||||||||||
Journal or Publication Title: | Physical Chemistry Chemical Physics | ||||||||||||
Publisher: | Royal Society of Chemistry | ||||||||||||
ISSN: | 1463-9076 | ||||||||||||
Official Date: | 14 July 2019 | ||||||||||||
Dates: |
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Volume: | 21 | ||||||||||||
Number: | 26 | ||||||||||||
Page Range: | pp. 14394-14406 | ||||||||||||
DOI: | 10.1039/c8cp07061j | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||||||
Date of first compliant deposit: | 12 February 2019 | ||||||||||||
Date of first compliant Open Access: | 19 March 2019 | ||||||||||||
RIOXX Funder/Project Grant: |
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