title: Electron and nuclear dynamics following ionisation of modified bismethylene-adamantane.
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.
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Morgane
authors.initials: M
authors.lastname: Vacher
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Fabio E A
authors.initials: FE
authors.lastname: Albertani
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Andrew J
authors.identifier: 0000-0002-1014-5225
authors.initials: AJ
authors.lastname: Jenkins
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Iakov
authors.initials: I
authors.lastname: Polyak
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Bearpark
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Michael A
authors.initials: MA
authors.lastname: Robb