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Issue 25, 2015
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Comparing the electronic relaxation dynamics of aniline and d7-aniline following excitation at 272–238 nm

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Abstract

Femtosecond time-resolved photoelectron spectroscopy experiments have been used to compare the electronic relaxation dynamics of aniline and d7-aniline following photoexcitation in the range 272–238 nm. Together with the results of recent theoretical investigations of the potential energy landscape [M. Sala, O. M. Kirkby, S. Guérin and H. H. Fielding, Phys. Chem. Chem. Phys., 2014, 16, 3122], these experiments allow us to resolve a number of unanswered questions surrounding the nonradiative relaxation mechanism. We find that tunnelling does not play a role in the electronic relaxation dynamics, which is surprising given that tunnelling plays an important role in the electronic relaxation of isoelectronic phenol and in pyrrole. We confirm the existence of two time constants associated with dynamics on the 11πσ* surface that we attribute to relaxation through a conical intersection between the 11πσ* and 11ππ* states and motion on the 11πσ* surface. We also present what we believe is the first report of an experimental signature of a 3-state conical intersection involving the 21ππ*, 11πσ* and 11ππ* states.

Graphical abstract: Comparing the electronic relaxation dynamics of aniline and d7-aniline following excitation at 272–238 nm

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Publication details

The article was received on 31 Mar 2015, accepted on 13 May 2015 and first published on 14 May 2015


Article type: Paper
DOI: 10.1039/C5CP01883H
Citation: Phys. Chem. Chem. Phys., 2015,17, 16270-16276
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    Comparing the electronic relaxation dynamics of aniline and d7-aniline following excitation at 272–238 nm

    O. M. Kirkby, M. Sala, G. Balerdi, R. de Nalda, L. Bañares, S. Guérin and H. H. Fielding, Phys. Chem. Chem. Phys., 2015, 17, 16270
    DOI: 10.1039/C5CP01883H

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