Parkes, Michael A;
Worth, Graham A;
(2024)
The “simple” photochemistry of thiophene.
The Journal of Chemical Physics
, 161
(11)
, Article 114305. 10.1063/5.0226105.
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Abstract
The static gas-phase (“simple”) ultraviolet absorption spectrum of thiophene is investigated using a combination of a vibronic coupling model Hamiltonian with multi-configuration time-dependent Hartree quantum dynamics simulations. The model includes five states and all 21 vibrations, with potential surfaces calculated at the complete active space with second-order perturbation level of theory. The model includes terms up to eighth-order to describe the diabatic potentials. The resulting spectrum is in excellent agreement with the experimentally measured spectrum of Holland et al. [Phys. Chem. Chem. Phys. 16, 21629 (2014)]. The, until now not understood, spectral features are assigned, with a combination of strongly coupled vibrations and vibronic coupling between the states giving rise to a progression of triplets on the rising edge of the broad spectrum. The analysis of the underlying dynamics indicates that population transfer between all states takes place on a sub-100 fs timescale, with ring-opening occurring at longer times. The model thus provides a starting point for further investigations into the complicated photo-excited dynamics of this key hetero-aromatic molecule.
| Type: | Article |
|---|---|
| Title: | The “simple” photochemistry of thiophene |
| Location: | United States |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1063/5.0226105 |
| Publisher version: | http://dx.doi.org/10.1063/5.0226105 |
| Language: | English |
| Additional information: | © 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/5.0226105 |
| 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/10198988 |
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