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

文献信息

发布日期 2015-05-14
DOI 10.1039/C5CP01883H
影响因子 3.676
作者

Oliver M. Kirkby, Matthieu Sala, Garikoitz Balerdi, Rebeca de Nalda, Luis Bañares, Stéphane Guérin, Helen H. Fielding


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摘要

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.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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