Electron and nuclear dynamics following ionisation of modified bismethylene-adamantane.
Faraday Discuss
; 194: 95-115, 2016 12 16.
Article
in En
| MEDLINE
| ID: mdl-27722360
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.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Faraday Discuss
Journal subject:
QUIMICA
Year:
2016
Document type:
Article
Affiliation country:
United kingdom