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Published on: October 18, 2018
Unraveling the Spectroscopy of the Phenalenyl Radical
Zachariah D Levey1, Benjamin A Laws1, Christopher S Hansen1
1School of Chemistry, University of New South Wales, Sydney, New South Wales 2052, Australia.
Abstract:
Jet-cooled excitation spectra of the phenalenyl radical are obtained using resonance enhanced multiphoton ionization. The excitation spectra reveal previously unobserved transitions, up to 17,000 cm-1 above the D1 origin, including transitions to electronically forbidden A2 ″ electronic states. A quasi-diabatic approach is applied to construct a vibronic Hamiltonian, including both Jahn-Teller and pseudo-Jahn-Teller interactions, between seven excited electronic surfaces. This is employed to calculate the electronic excitation spectrum of the phenalenyl radical in its entirety, providing vibronic assignments and spectral parameters to help decode the spectroscopy of this key radical.
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