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High resolution vacuum ultraviolet pulsed field ionization photoelectron band for OCS+(X 2Π): An experimental and theoretical study

Abstract : The vacuum ultraviolet pulsed field ionization photoelectron (PFI-PE) band for OCS+(X 2Π) in the energy region of 11.09-11.87 eV has been measured using high resolution monochromatized synchrotron radiation. The ionization energies (IEs) for the formation of the (0,0,0) X 2Π3/2 and (0,0,0) 2Π1/2 states of OCS+ are determined to be 11.1831±0.0005 and 11.2286±0.0005 eV, respectively, yielding a value of 367±1.2 cm−1 for the spin-orbit splitting. Using the internally contracted multireference configuration interaction approach, three-dimensional potential energy functions (PEFs) for the OCS+(X 2Π) state have been generated and used in the variational Renner-Teller calculations of the vibronic states. The energies of all vibronic states (J = P) for J = 1/2, 3/2, 5/2, and 7/2 have been computed in the energy range of ≈ 4000 cm−1 above the IE[OCS+(X 2Π3/2)] for the assignment of the experimental spectrum. By a minor modification of the ab initio PEFs, good correlations are found between the experimental and theoretical Renner-Teller structures. Similar to the PFI-PE bands for CO2+(X 2Πg) and CS2+(X 2Πg), weak transitions have been detected in the PFI-PE band for OCS+(X 2Π), which are forbidden in the Franck-Condon approximation. The nonvanishing single-photon ionization cross sections involving the excitation of the bending vibrational modes of OCS+, CO2+, and CS2+, in their ground electronic states are attributed to the symmetries of the geometry-dependent electronic transition dipole operator components.
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https://hal-upec-upem.archives-ouvertes.fr/hal-00737277
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Submitted on : Monday, October 1, 2012 - 2:33:10 PM
Last modification on : Wednesday, February 26, 2020 - 7:06:08 PM

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S. Stimson, C. Y. Ng, C.-W. Hsu, P. Heimann, C. Destandau, et al.. High resolution vacuum ultraviolet pulsed field ionization photoelectron band for OCS+(X 2Π): An experimental and theoretical study. Journal of Chemical Physics, American Institute of Physics, 1998, 108 (15), pp.6205--6214. ⟨10.1063/1.476027⟩. ⟨hal-00737277⟩

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