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Identification of a ¹Δ [delta] u - ¹Σ [sigma] ⁺g transition of CS₂ in the near ultraviolet

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Title: Identification of a ¹Δ [delta] u - ¹Σ [sigma] ⁺g transition of CS₂ in the near ultraviolet
Author: Malm, David Nelson
Degree: Master of Science - MSc
Program: Chemistry
Copyright Date: 1972
Subject Keywords Absorption spectra.
Issue Date: 2011-04-11
Publisher University of British Columbia
Series/Report no. UBC Retrospective Theses Digitization Project [http://www.library.ubc.ca/archives/retro_theses/]
Abstract: The strongest features in the absorption spectrum of CS₂ in the region 2900Å to 3500Å are identified, from temperature studies, as a π → π* ¹Δu - ¹Σ⁺g transition, where the Renner-Teller effect has split the ¹Δu state into ¹B₂ and ¹A₂ component states of a bent molecule. Analysis of some of the least severely perturbed bands of the ¹B₂ - ¹Σ⁺g transitions (3300 - 2900Å) shows that they form a parallel-polarized progression in the bending vibration, to an upper state with r(C - S) = 1.54₄Å, < SĈS = 163°, and a barrier to linearity of ~ 1400 cm⁻¹. Two hitherto unrecognized progressions of 'hot' bands, a weak vibronic ∏ - ∏ and a stronger vibronic Δ - Δ progression in the region 3300Å to 3500Å, are assigned to the ¹A₂ - ¹Σ⁺g transiton. This is a new type of transition, which does not appear in cold absorption, but whose 'hot' bands can obtain an amount of intensity (proportional to K²) through Renner-Teller mixing.
Affiliation: Science, Faculty of
URI: http://hdl.handle.net/2429/33491
Scholarly Level: Graduate

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