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- W2112264628 abstract "Partially rotationally resolved pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the three isotopomers (35Cl2, 35Cl37Cl, and 37Cl2) of Cl2 have been recorded in the wavenumber ranges 92 500–96 500 cm−1, corresponding to transitions to the low vibrational levels of the X+ 2Πg (Ω = 3/2, 1/2) ground state of ${rm Cl}_2^+$ Cl 2+, and 106 750–115 500 cm−1, where the $mathrm{a}^+ ^4Sigma _mathrm{u}^-break leftarrow mathrm{X} ^1Sigma _mathrm{g}^+$a+Σu−4←XΣg+1, $mathrm{A}^+ ^2Pi _mathrm{u}leftarrow mathrm{X} ^1Sigma _mathrm{g}^+$A+Πu2←XΣg+1, and $mathrm{B}^+ ^2Delta _mathrm{u}leftarrow mathrm{X} ^1Sigma _mathrm{g}^+$B+Δu2←XΣg+1 band systems overlap with transitions to high vibrational levels (v+ > 25) of the X+ state. The observation of Franck-Condon-forbidden transitions to vibrational levels of the X+ state of the cation with v+ ⩾ 25 is rationalized by a mechanism involving vertical excitation of predissociative Rydberg states of mixed singlet-triplet character with an A+ ion core which are coupled to Rydberg states converging to high-v+ levels of the X+ state. The same mechanism is proposed to also be responsible for the observation of Cl+ − Cl− ion pairs and quartet states in the photoionization of Cl2. The potential energy function of the X+ state of ${rm Cl}_2^+$ Cl 2+ was determined in a direct fit to the experimental data. Transitions to vibrational levels of the A+ 2Πu, 3/2 and B+ 2Δu, 3/2 states of ${rm Cl}_2^+$ Cl 2+ could be identified using the results of a recent analysis of the strong perturbation between the A+ 2Πu, 3/2 and B+ 2Δu, 3/2 states of ${rm Cl}_2^+$ Cl 2+ observed in the A+ − X+ band system [Gharaibeh et al., J. Chem. Phys. 137, 194317 (2012)]10.1063/1.4765334, and transitions to several vibrational levels of the upper spin-orbit component (2Πu, 1/2) of the A+ state were detected in the photoelectron spectrum of ${rm Cl}_2^+$ Cl 2+. The $mathrm{a}^+ ^4Sigma _mathrm{u}^-leftarrow mathrm{X} ^1Sigma _mathrm{g}^+$a+Σu−4←XΣg+1 photoelectron band system, which is nominally forbidden by single-photon ionization from the ground state was also observed for the first time and its vibrational and spin-orbit structures were analyzed. The $^4Sigma _mathrm{u}^-$Σu−4 state is split into two spin-orbit components with Ω = 1/2 and Ω = 3/2, separated by 37.5 cm−1. The vibrational energy level structure of both components is regular, which indicates that the splitting results from the interaction with one or more distant ungerade Ω = 1/2 or Ω = 3/2 electronic states." @default.
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- W2112264628 date "2013-07-15" @default.
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- W2112264628 title "The X+ 2Πg, A+ 2Πu, B+ 2Δu, and $mathrm{a}^+ ^4Sigma _{mathrm{u}}^-$a+Σu−4 electronic states of ${rm Cl}_2^+$ Cl 2+ studied by high-resolution photoelectron spectroscopy" @default.
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- W2112264628 doi "https://doi.org/10.1063/1.4812376" @default.
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