Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part II: Theoretical investigation of oxalyl chloride

Bokarev, Sergey I.; Пупышев, В.И.; Godunov, I. A.

doi:10.1016/j.jms.2009.05.004

Cited by 11 publications

(33 citation statements)

References 52 publications

(128 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We found the wave functions of the oxalyl chloridefluoride in the excited electronic states to be strongly multiconfigurational especially for the structures skewed relative to C-C bond similar to the (COF) 2 and (COCl) 2 molecules [2,3]. In some cases, even in minima the wave function can be represented by two or three configurations with comparable weights.…”

Section: Computational Detailsmentioning

confidence: 89%

“…As in glyoxal (see, e.g., [13]), oxalyl fluoride [3] and oxalyl chloride [2], the four lowest excited states of oxalyl chloridefluoride are two singlet and two triplet states, which arise from n ? p* excitations.…”

Section: Computational Detailsmentioning

confidence: 99%

“…For oxalyl chloridefluoride, there are no experimental data on geometries of conformers in the ground electronic state. The comparison of calculated values could be made only with geometric parameters of oxalyl fluoride (COF) 2 and oxalyl chloride (COCl) 2 obtained experimentally [29,30] or theoretically [2,3]. In general, if the CCSD(T)/ cc-pVTZ or cc-pVQZ values are compared, the respective geometric parameters of CFO, CClO fragments of COCl-COF, (COF) 2 , and (COCl) 2 molecules are very similar.…”

Section: Geometric Parametersmentioning

confidence: 99%

“…The present work is the fifth part of our systematic investigations of the structures and conformational dynamics of oxalyl halide molecules (COHal) 2 in the ground and lowest excited electronic states. 1 The first four parts are devoted to the experimental and theoretical investigations of oxalyl chloride (COCl-COCl) [1,2] and oxalyl fluoride (COF-COF) [3,4].…”

Section: Introductionmentioning

confidence: 99%

“…1 The first four parts are devoted to the experimental and theoretical investigations of oxalyl chloride (COCl-COCl) [1,2] and oxalyl fluoride (COF-COF) [3,4].…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part V: Oxalyl chloridefluoride (COCl–COF)

2010

View full text Add to dashboard Cite

The structure and conformational dynamics of the COCl-COF molecule in the ground and lowest excited electronic states were investigated theoretically by the CASPT2/cc-pVTZ method. The equilibrium geometric parameters, harmonic vibrational frequencies, potential functions of internal rotation, and adiabatic transition energies were obtained. According to the results of calculations, the molecule in the ground electronic state exist as the trans and gauche (dOCCO *30-40°) conformers with a low potential barrier to gauche-gauche transition therefore it is impossible to exclude existence of the cis conformer (instead of gauche) with a very broad and flat potential minimum. For all the investigated excited electronic states of oxalyl chloridefluoride molecule calculations predicted the trans and cis conformers. The strong coupling of internal rotation around the C-C bond and non-planar vibrations of carbonyl fragments was found for the excited electronic states. The results of calculation were utilized for reanalysis of experimentalÃ 1 A 00 X 1 A 0 andã 3 A 00 X 1 A 0 vibronic spectra reported in King (J Mol Spectrosc 50:209-219 (1974), and ibid. 48:592-599 (1973)). The vibrational assignment that does not contradict the vibrational spectroscopy data and results of calculations was obtained.

show abstract

Section: Computational Detailsmentioning

confidence: 89%

Section: Computational Detailsmentioning

confidence: 99%

Section: Geometric Parametersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…1 The first four parts are devoted to the experimental and theoretical investigations of oxalyl chloride (COCl-COCl) [1,2] and oxalyl fluoride (COF-COF) [3,4].…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations