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Abstract
We report a theoretical investigation and elucidation of the x-ray absorption spectra of neutral benzene and of the benzene cation. The generation of the cation by multiphoton ultraviolet (UV) ionization as well as the measurement of
the carbon K-edge spectra of both species using a table-top high-harmonic generation (HHG) source are described in the companion experimental paper [M. Epshtein et al., J. Phys.
Chem. A., submitted. Available on ChemRxiv]. We show that the 1sC -> pi transition serves as a sensitive signature of the transient cation formation, as it occurs outside of the spectral window of the parent neutral species. Moreover, the presence
of the unpaired (spectator) electron in the pi-subshell of the cation and the high symmetry of the system result in significant differences relative to neutral benzene in the spectral features associated with the 1sC ->pi* transitions. High-level calculations using equation-of-motion coupled-cluster theory provide the interpretation of the experimental spectra and insight into the electronic structure of benzene and its cation.
The prominent split structure of the 1sC -> pi* band of the cation is attributed to the interplay between the coupling of the core -> pi* excitation with the unpaired electron
in the pi-subshell and the Jahn-Teller distortion. The calculations attribute most of
the splitting (~1-1.2 eV) to the spin coupling, which is visible already at the Franck-Condon structure, and estimate the additional splitting due to structural relaxation to
be around ~0.1-0.2 eV. These results suggest that x-ray absorption with increased resolution might be able to disentangle electronic and structural aspects of the Jahn-Teller
effect in benzene cation.
the carbon K-edge spectra of both species using a table-top high-harmonic generation (HHG) source are described in the companion experimental paper [M. Epshtein et al., J. Phys.
Chem. A., submitted. Available on ChemRxiv]. We show that the 1sC -> pi transition serves as a sensitive signature of the transient cation formation, as it occurs outside of the spectral window of the parent neutral species. Moreover, the presence
of the unpaired (spectator) electron in the pi-subshell of the cation and the high symmetry of the system result in significant differences relative to neutral benzene in the spectral features associated with the 1sC ->pi* transitions. High-level calculations using equation-of-motion coupled-cluster theory provide the interpretation of the experimental spectra and insight into the electronic structure of benzene and its cation.
The prominent split structure of the 1sC -> pi* band of the cation is attributed to the interplay between the coupling of the core -> pi* excitation with the unpaired electron
in the pi-subshell and the Jahn-Teller distortion. The calculations attribute most of
the splitting (~1-1.2 eV) to the spin coupling, which is visible already at the Franck-Condon structure, and estimate the additional splitting due to structural relaxation to
be around ~0.1-0.2 eV. These results suggest that x-ray absorption with increased resolution might be able to disentangle electronic and structural aspects of the Jahn-Teller
effect in benzene cation.
Supplementary materials
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