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 |
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Date Type: | Publication |
Status: | Published |
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: | 07 Nov 2023 02:45 |
URI: | https://orca.cardiff.ac.uk/id/eprint/110441 |
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