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Negative Ion Photoelectron Spectroscopy Confirms the Prediction of a Singlet Ground State for the 1,8-Naphthoquinone Diradical

Tijdschriftbijdrage - Tijdschriftartikel

Negative ion photoelectron (NIPE) spectra, with 193, 266, 300, and 355 nm photons, of the radical anion of 1,8-naphthoquinone (1,8-NQ•-) have been obtained at 20 K. The electron affinity of 1,8-NQ is determined from the first resolved peak in the NIPE spectrum to be 2.965 ± 0.005 eV. Franck-Condon factors (FCFs), calculated from the CASPT2/aug-cc-pVDZ optimized geometries, normal modes, and vibrational frequencies, successfully simulate the intensity and frequencies of the spectral features that are associated with the lowest two electronic states. The NIPE spectra of 1,8-NQ•- and the peak assignments, based on the computed FCFs, confirm the theoretical predictions that 1A1 is the ground state of 1,8-NQ and 3B2 is the first excited state. The spectra provide an experimental value of Δ EST = -0.6 kcal/mol, which is 2 kcal/mol smaller in magnitude than the (12/12)CASPT2/aug-cc-pVTZ calculated value of Δ EST = -2.6 kcal/mol.
Tijdschrift: Journal of Physical Chemistry. A
ISSN: 1089-5639
Issue: 14
Volume: 123
Pagina's: 3142 - 3148
Aantal pagina's: 7
Jaar van publicatie:2019