Gómez, S;
Ibele, LM;
González, L;
(2019)
The 3s Rydberg state as a doorway state in the ultrafast dynamics of 1,1-difluoroethylene.
Physical Chemistry Chemical Physics
, 21
(9)
pp. 4871-4878.
10.1039/c8cp07766e.
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Abstract
The deactivation dynamics of 1,1-difluoroethylene after light excitation is studied within the surface hopping formalism in the presence of 3s and 3p Rydberg states using multi-state second order perturbation theory (MS-CASPT2). Due to the proximity of the Rydberg π-3s state with the ππ* state, the states are mixed favoring ultrafast exchange of population via a conical intersection that closely resembles the equilibrium structure. After excitation, it is found that the π-3s state acts as a doorway state, trapping the population and delaying internal conversion to the ππ* state, from which deactivation to the closed-shell ground state takes place. Besides the conical intersection between the π-3s and ππ* states, five additional conical intersections between the ππ* state and the ground state are found, indicating that after the system is excited, it stretches the C[double bond, length as m-dash]C bond before it twists and pyramidalizes at any of the carbon atoms, in the spirit of a hula-twist mechanism.
| Type: | Article |
|---|---|
| Title: | The 3s Rydberg state as a doorway state in the ultrafast dynamics of 1,1-difluoroethylene |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1039/c8cp07766e |
| Publisher version: | https://doi.org/10.1039/c8cp07766e |
| Language: | English |
| Additional information: | This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/). |
| UCL classification: | UCL 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/10084436 |
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