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• W2009895104 abstract "The pulsed-field-ionization zero-kinetic-energy photoelectron spectra of allene (C3H4) and perdeuterated allene have been recorded from the first adiabatic ionization energy up to 2200 cm−1 of internal energy in the cations at a resolution sufficient to observe the full rotational structure. The intensity distributions in the spectra are dominated by vibrational progressions in the torsional mode, which were analyzed in the realm of a two-dimensional model of the E⊗(b1⊕b2) Jahn–Teller effect in the allene cation [C. Woywod and W. Domcke, Chem. Phys. 162, 349 (1992)]. Whereas the rotational structure of the transitions to the lowest torsional levels (00 and 41) are regular and can be qualitatively analyzed in terms of a simple orbital ionization model, the rotational structure of the spectra of the 42 and 43 levels are strongly perturbed. The photoelectron spectrum of C3H4 also reveals several weak vibrational bands in the immediate vicinity of these levels that are indicative of (ro)vibronic perturbations. A slight broadening of the transitions to the 41 levels compared to that of the vibronic ground state and the increase of the number of sharp features in the rotational structure of the spectrum of the 42 level point at the importance of large-amplitude motions not considered in previous treatments of the Jahn–Teller effect in the allene cation." @default.
• W2009895104 created "2016-06-24" @default.
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• W2009895104 date "2009-01-21" @default.
• W2009895104 modified "2023-10-03" @default.
• W2009895104 title "Rotationally resolved photoelectron spectroscopic study of the Jahn–Teller effect in allene" @default.
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• W2009895104 doi "https://doi.org/10.1063/1.3056385" @default.
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