Issue 26, 2019

New insights into the dissociation dynamics of methylated anilines


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.

Graphical abstract: New insights into the dissociation dynamics of methylated anilines

Supplementary files

Article information

Article type
15 Nov 2018
07 Feb 2019
First published
12 Mar 2019
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2019,21, 14394-14406

New insights into the dissociation dynamics of methylated anilines

N. C. Cole-Filipiak and V. G. Stavros, Phys. Chem. Chem. Phys., 2019, 21, 14394 DOI: 10.1039/C8CP07061J

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