Robertson, C;
Worth, GA;
(2018)
Modelling the non-radiative singlet excited state isomerization of diphenyl-acetylene: A vibronic coupling model.
Chemical Physics
, 510
pp. 17-29.
10.1016/j.chemphys.2018.04.020.
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Abstract
Tolane (diphenyl-acetylene) is the smallest component of macromolecular arrays known as dendrimers that have interesting energy transport properties after photo-excitation. In this paper, a vibronic coupling Hamiltonian is set up to describe the initial isomerization of this molecule. The calculated absorption spectrum is in good agreement with experiment, with the ordering of states and energies from MRCI-DFT calculation. The focus of the study is the pathway for photo-excited isomerisation from the linear geometry at the Frank-Condon point to a trans-structure. The model shows that the origin of the excited-state minimum for the trans-isomer is due to stabilisation of a high lying state. Quantum dynamics calculations using the MCTDH algorithm show the model agrees with experiment that isomerisation only occurs at high temperature. It also suggests that internal conversion to the S1 global minima happens via second order coupling terms, which can explain the observed picosecond timescales.
| Type: | Article |
|---|---|
| Title: | Modelling the non-radiative singlet excited state isomerization of diphenyl-acetylene: A vibronic coupling model |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1016/j.chemphys.2018.04.020 |
| Publisher version: | http://dx.doi.org/10.1016/j.chemphys.2018.04.020 |
| Language: | English |
| Additional information: | This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. |
| Keywords: | Tolane, Diphenyl-acetylene, Dendrimer photochemistry, Vibronic coupling model, MCTDH |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices 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/10053414 |
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