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Threshold photoionization spectra of toluene+ and phenylsilane+ using the new pulsed field ionization technique resolve internal rotor states. As in the neutral S0 and S1 states, sixfold barriers to internal rotation are small in the cations, < 25 cm-1. Ab initio calculations support a donor-acceptor model that qualitatively explains why all sixfold barriers are small while some threefold barriers are much larger.
Kueih-Tzu Lu andJames C. Weisshaar
"Understanding barriers to internal rotation in toluene, phenylsilane, and their cations", Proc. SPIE 2124, Laser Techniques for State-Selected and State-to-State Chemistry II, (17 June 1994); https://doi.org/10.1117/12.178109
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Kueih-Tzu Lu, James C. Weisshaar, "Understanding barriers to internal rotation in toluene, phenylsilane, and their cations," Proc. SPIE 2124, Laser Techniques for State-Selected and State-to-State Chemistry II, (17 June 1994); https://doi.org/10.1117/12.178109