Vacher, Morgane, Albertani, Fabio E. A., Jenkins, Andrew J., Polyak, Iakov  ORCID: https://orcid.org/0000-0002-2894-0657, Bearpark, Michael J. and Robb, Michael A.
2016.
Electron and nuclear dynamics following ionisation of modified bismethylene-adamantane.
Faraday Discussions
194
, pp. 95-115.
10.1039/C6FD00067C
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Abstract
We have simulated the coupled electron and nuclear dynamics using the Ehrenfest method upon valence ionisation of modified bismethylene-adamantane (BMA) molecules where there is an electron transfer between the two π bonds. We have shown that the nuclear motion significantly affects the electron dynamics after a few fs when the electronic states involved are close in energy. We have also demonstrated how the non-stationary electronic wave packet determines the nuclear motion, more precisely the asymmetric stretching of the two π bonds, illustrating “charge-directed reactivity”. Taking into account the nuclear wave packet width results in the dephasing of electron dynamics with a half-life of 8 fs; this eventually leads to the equal delocalisation of the hole density over the two methylene groups and thus symmetric bond lengths.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry |
| Publisher: | Royal Society of Chemistry |
| ISSN: | 1359-6640 |
| Funders: | EPSRC |
| Date of First Compliant Deposit: | 3 April 2018 |
| Date of Acceptance: | 13 May 2016 |
| Last Modified: | 20 Nov 2024 01:45 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/110441 |
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