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Title: The intensity of forbidden torsional transitions in electronic spectra of molecules with a 6-fold barrier: Application to toluenes

Franck-Condon forbidden transitions involving methyl rotor modes are seen in the S{sub 1} ← S{sub 0} spectrum of toluene and toluene-like molecules. The strongest of these rotor transitions (m{sup ″} = 1 → m{sup ′} = 2, m{sup ″} = 0 → m{sup ′} = 3a{sub 1}{sup ″}, and m{sup ″} = 1 → m{sup ′} = 4) have been shown by Walker et al. [J. Chem. Phys. 102, 8718 (1995)] to gain intensity through the rotor equivalent of the Herzberg-Teller mechanism. Despite the m{sup ″} = 0 → m{sup ′} = 3a{sub 2}{sup ″} transition being forbidden in this formalism, it is sporadically observed. We show that this transition derives oscillator strength from incomplete mixing of the −3 and +3 free rotor basis states due to torsion-rotation coupling. Calculations demonstrate that this mechanism quantitatively explains the intensities observed for toluene, including their temperature dependence. Because the −3/+3 mixing is weakest when the torsional barrier height, V{sub 6}, is small, the m{sup ″} = 0 → m{sup ′} = 3a{sub 2}{sup ″} transition increases in intensity as |V{sub 6}| decreases. The temperature and |V{sub 6}| dependencies explain why reports of the 0 → 3a{sub 2}{sup ″} transition have been intermittent. The torsion-rotation coupling mechanism is predicted to also give significant intensity to m =more » 0 → m = 6a{sub 2}{sup ′} transitions relative to m = 0 → m = 6a{sub 1}{sup ′} transitions and to provide intensity to 0 → 3a{sub 2} transitions in molecules with a 3-fold (V{sub 3}) barrier. Comparison between the observed and calculated rotor band contours shows, unexpectedly, that the 3a{sub 1}{sup ″} constants fail to predict the 3a{sub 2}{sup ″} contour despite these two states being derived from the same free rotor basis states. Comparison with the observed spectrum also reveals differences in the separation of the S{sub 1} 3a{sub 2}{sup ″} and 3a{sub 1}{sup ″} levels. The V{sub 6} value determined from analysis of the high resolution, rotationally resolved m{sup ″} = 0 → m{sup ′} = 3a{sub 1}{sup ″} spectrum overestimates the 3a{sub 2}{sup ″}–3a{sub 1}{sup ″} separation by 0.6 cm{sup −1}. We postulate that this may be due to torsion-vibration coupling. The observed toluene torsion-rotation contours have been modeled to provide estimates of the rotational constants for several of the torsional states.« less
Authors:
; ;  [1]
  1. School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia)
Publication Date:
OSTI Identifier:
22253095
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 15; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COUPLING; FORBIDDEN TRANSITIONS; OSCILLATOR STRENGTHS; ROTATION; SPECTRA; TEMPERATURE DEPENDENCE; TOLUENE