Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part I: Reanalysis of the 3680 Å and 4100 Å absorption systems of oxalyl chloride

• Published in: Journal of molecular spectroscopy Vol. 255; no. 1; pp. 39 - 44
• Main Authors: Godunov, I.A., Yakovlev, N.N., Bokarev, S.I., Abramenkov, A.V., Maslov, D.V.
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.05.2009
• Subjects: Internal rotation; Oxalyl chloride; Vibronic spectra; Vibronic spectra; Oxalyl chloride; Internal rotation
• ISSN: 0022-2852; 1096-083X
• DOI: 10.1016/j.jms.2009.02.019

The vapor-phase absorption spectrum of oxalyl chloride in the 3000–4180 Å region has been re-examined at high resolution. Singlet–singlet A ˜ 1 A u ← X ˜ 1 A g and singlet–triplet a ˜ 3 A u ← X ˜ 1 A g electronic transitions of the trans-conformer found in the spectrum are in agreement with earlier works [W.J. Balfour, G.W. King, J. Mol. Spectrosc. 26 (1968) 384–397; ibid. 27 (1968) 432–442]. Torsion levels of trans-oxalyl chloride in the ground X ˜ 1 A g and excited A ˜ 1 A u and a ˜ 3 A u states were found for the first time. Ab initio calculations of structures for conformers of oxalyl chloride in the ground and lowest excited electronic states explain the absence of second conformer transitions in the vibronic absorption spectrum.