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• W2022085185 abstract "The absorption spectrum of jet-cooled CS2 has been photographed between 50 500 and 65 500 cm−1 at a resolution limit of 0.008 Å. Ab initio calculations are carried out to estimate the energy of the lower Rydberg states of ionic cores ...2π3g, ...2π3u, and ...5σu, as well as those belonging to the doubly excited configuration ...2π2g3π2u. Assigned electronic states include the ...2π3g4s 1Πg (with vibronic bands 201 and 2n0, n=1,3,5,7, observed thanks to a concurrent of Herzberg–Teller intensity borrowing and Renner–Teller intensity redistribution) and ...2π3g4p 1,3Πu, and 3Σu− (observed bands being the electronic origin, 110 and 220 bands). Model calculations of Renner–Teller interaction in the 1Π states are performed leading to ε and ω2 parameter values. In the case of the 4p 1Πu state, Fermi resonance between the v1′=1 level and the v2′=2 RT-split levels of Πu vibronic symmetry, is also taken into account. The rotational band contours of the origin bands of the whole set of the ...2π3g4p Rydberg transitions excited by one or three photons are calculated using a model based on Hund’s case (e) representation. The calculated band contours, wave numbers, and relative intensities are in excellent agreement with the observations of the present vuv absorption spectrum, and the multiphoton (3+1) ionization spectrum of Baker et al. [J. Chem. Phys. 103, 2436 (1995)] provided that in the latter, the 1Σ+u state is reassigned as 3Σu−. Fitted values of the 4p quantum defects and of the 4pπ(1Σ+u)/4pσ(1Πu) transition moment ratio are found to be perfectly consistent with the ab initio calculation results. Possible assignments of 3d transitions in the present and previous vuv absorption spectra as well as in recent multiphoton ((1+1′)+1) ionization spectra of CS2 below 65 500 cm−1 are also discussed in the light of the present calculation results." @default.
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• W2022085185 date "1996-05-15" @default.
• W2022085185 modified "2023-10-18" @default.
• W2022085185 title "The high resolution absorption spectrum of jet-cooled CS2 between 50 500 and 65 500 cm−1" @default.
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• W2022085185 doi "https://doi.org/10.1063/1.471486" @default.
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