Electronic Spectrum of α‑Hydrofulvenyl Radical (C6H7), and a Simple and Accurate Recipe for Predicting Adiabatic Ionization Energies of Resonance-Stabilized Hydrocarbon Radicals

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-09, Vol.128 (38), p.8123-8136
• Main Authors: Flores, Jonathan, Ruscitti, Massimo, Khani, Sima, Reilly, Neil J.
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c04746

Using a combination of resonant two-photon two-color ionization (R2C2PI) and laser-induced fluorescence/dispersed fluorescence spectroscopy, we have examined the à  2 A″ ← X̃  2A″ transition of the resonance-stabilized α-hydrofulvenyl radical, produced from methylcyclopentadiene dimer in a jet-cooled discharge. Like the related 1,4-pentadienyl and cyclohexadienyl radicals, the α-hydrofulvenyl Ã-state lifetime is orders of magnitude shorter than the predicted f-value implies, indicative of rapid nonradiative decay. The transition is fully allowed by symmetry but considerably weakened by transition moment interference. Intensity borrowing among a′ modes brings about static (i.e., Condon) and vibronic (i.e., Herzberg–Teller) moments of similar size, the result being a spectrum substantially less origin-dominated than is usually observed for extensively delocalized radicals. Twenty à -state modes and twelve X̃ -state modes are identified with high confidence and assignments for several others are suggested. In addition, from a series of two-color appearance potential scans with the à -state zero-point level serving as an intermediate, we obtain a field-free adiabatic ionization energy (AIE) of 7.012(1) eV. For a set of 21 resonance-stabilized radicals bearing 5 to 11 carbon atoms, it emerges that the field-free AIE obtained by R2C2PI methods under jet-cooled conditions lies very close to the average of B3LYP/6-311G++(d,p) (with harmonic zero-point energy) and CBS-QB3 0 K calculations, with a mean absolute deviation of only 0.010(7) eV (approximately 1 kJ/mol). On average, this represents a nearly 10-fold improvement in accuracy over CBS-QB3 predictions for the same set of radicals.