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Issue 9, 2019
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The 3s Rydberg state as a doorway state in the ultrafast dynamics of 1,1-difluoroethylene

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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.

Graphical abstract: The 3s Rydberg state as a doorway state in the ultrafast dynamics of 1,1-difluoroethylene

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Publication details

The article was received on 20 Dec 2018, accepted on 13 Feb 2019 and first published on 13 Feb 2019


Article type: Paper
DOI: 10.1039/C8CP07766E
Phys. Chem. Chem. Phys., 2019,21, 4871-4878
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    The 3s Rydberg state as a doorway state in the ultrafast dynamics of 1,1-difluoroethylene

    S. Gómez, L. M. Ibele and L. González, Phys. Chem. Chem. Phys., 2019, 21, 4871
    DOI: 10.1039/C8CP07766E

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