Ultrafast relaxation from 1La to 1Lb in pyrene: a theoretical study
| Autor: | Sebastian Reiter, Matthias K. Roos, Regina de Vivie-Riedle |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
010304 chemical physics
Basis (linear algebra) Chemistry Wave packet Quantum dynamics General Physics and Astronomy Surface hopping Electronic structure Conical intersection 010402 general chemistry 01 natural sciences 0104 chemical sciences Excited state 0103 physical sciences Statistical physics Relaxation (approximation) Physical and Theoretical Chemistry |
| Zdroj: | Chemical Physics. 515:586-595 |
| ISSN: | 0301-0104 |
| DOI: | 10.1016/j.chemphys.2018.08.002 |
| Popis: | Pyrene and its photophysics have been extensively studied, especially experimentally. Yet to this day there is no conclusive theoretical description of the relaxation from the photo-accessible 1 L a state to the fluorescent 1 L b state, which is partly due to the challenge of adequately modeling both states without over-stabilizing one or the other. We first compare several quantum chemical methods to find the best model that offers a good trade-off between a balanced description of both states and computational effort. On the basis of the selected electronic structure method, we simulate this relaxation process with two state-of-the-art dynamical techniques. We perform wave packet propagations in reduced dimensions and full-dimensional on-the-fly surface hopping to corroborate our choice of coordinates and obtain a more complete picture of the relaxation mechanism. Our results confirm the important role of a conical intersection between the two excited states that has been postulated in the literature. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Full Text from ScienceDirect