Kirkby, OM;
Sala, M;
Balerdi, G;
de Nalda, R;
Bañares, L;
Guérin, S;
Fielding, HH;
(2015)
Comparing the electronic relaxation dynamics of aniline and d 7 -aniline following excitation at 272–238 nm.
Physical Chemistry Chemical Physics
, 17
(25)
pp. 16270-16276.
10.1039/C5CP01883H.
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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.
| Type: | Article |
|---|---|
| Title: | Comparing the electronic relaxation dynamics of aniline and d 7 -aniline following excitation at 272–238 nm |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1039/C5CP01883H |
| Publisher version: | http://dx.doi.org/10.1039/C5CP01883H |
| Language: | English |
| Additional information: | Copyright © Royal Society of Chemistry 2015. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/1469052 |
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