Relaxation dynamics of aniline in methanol: the photoionization channel

Abstract

The relaxation of aniline after excitation at 267 and 200 nm (4.6 and 6.2 eV) in methanol solutions has been explored by fs time-resolved experiments and the observations interpreted using ab initio calculations on the excited states of aniline–methanol clusters. In contrast to what has been reported under aqueous solvation, excitation at 267 nm does not induce ionization of the molecule and only a photophysical relaxation route is operative. The computational results allow us to rationalize this observation in terms of the different nature that the Rydberg transition, responsible for the electron ejection, presents in analogous N–H⋯O structures seen in methanol and water clusters. On the other hand, ionization of aniline via the direct ejection of an electron into the solvent is identified in methanol following 200 nm excitation, a mechanism analogous to that found in water at this energy.

Graphical abstract: Relaxation dynamics of aniline in methanol: the photoionization channel

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Article information

Article type
Paper
Submitted
10 Mar 2025
Accepted
02 Jul 2025
First published
03 Jul 2025
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2025, Advance Article

Relaxation dynamics of aniline in methanol: the photoionization channel

R. Montero, I. Lamas, M. Fernández-Fernández, A. W. Prentice, D. Townsend, M. J. Paterson and A. Longarte, Phys. Chem. Chem. Phys., 2025, Advance Article , DOI: 10.1039/D5CP00937E

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