Issue 5, 2016

Electronic structure of the para-benzoquinone radical anion revisited

Abstract

Photoinduced dynamics of the para-benzoquinone anion features a subtle interplay between autodetachment and non-adiabatic transitions involving a dense manifold of resonances. We report the results of a multistate multireference perturbation theory study of the electronic structure of the para-benzoquinone anion in the ground, several low-lying excited electronic states, and in the lowest electron-detached state (the ground state of the neutral molecule). The electronic structure calculations revealed non-planar equilibrium geometry of the 2Au excited state of the anion, but the effects of non-planarity on the shape of the absorption spectrum are found to be minor. Despite the large differences in the vertical excitation energies for the two lowest bright excited states, 2Au (2.55 eV) and 2B3u (2.93 eV), the simulated absorption spectra significantly overlap for the photon energies below 2.7 eV. Relevant minimum energy crossing points have been located using the CASSCF method. Excited-state deactivation channels are discussed in the context of accurate energetics and recent spectroscopic studies of the para-benzoquinone anion.

Graphical abstract: Electronic structure of the para-benzoquinone radical anion revisited

Supplementary files

Article information

Article type
Paper
Submitted
25 Oct 2015
Accepted
11 Dec 2015
First published
17 Dec 2015

Phys. Chem. Chem. Phys., 2016,18, 3454-3462

Author version available

Electronic structure of the para-benzoquinone radical anion revisited

A. A. Kunitsa and K. B. Bravaya, Phys. Chem. Chem. Phys., 2016, 18, 3454 DOI: 10.1039/C5CP06476G

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