A transferable general valence force field for oxalyl halides: fourier transform infrared spectral analysis of oxalyl chloride isolated in cryogenic rare gas matrices

Davidovics, G.; Monnier, M.; Schroeder, W. H.; Verlaque, P.; Pourcin, J.; Bodot, Hubert

doi:10.1016/0022-2860(89)85164-6

Cited by 6 publications

(5 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since the stronger peak of (CO 35 Cl) 2 is observed at 0.4 cm -1 lower in energy than the weaker band of CO 35 ClCO 37 Cl, the vibrational energy and the isotope splitting in the S 0 state are estimated to be 634 and 1.0 cm -1 , respectively. These values are in good agreement with those determined in cryogenic rare gas matrices. , In the same manner, two peaks on the high-energy side of the band are assigned to the C−C stretching bands. The shift is also 7 cm -1 , and the peak separation is 0.6 cm -1 .…”

Section: Resultssupporting

confidence: 87%

“…The fundamental frequency for ν 7 is then estimated to be 102 cm -1 . It is approximately twice that of the S 0 state (55 cm -1 ). , For several carbonyl molecules, the C−CHO torsion frequencies are larger in the excited state than in the ground state . It can be attributed to the increase of π conjugation in the excited state, which stabilizes the planar structure and increases the fundamental frequency.…”

Section: Resultsmentioning

confidence: 97%

“…They are believed to arise from 35 Cl and 37 Cl isotopes. The isotope splitting is approximately 1 cm -1 in the S 0 state although it varies with the vibrational modes. , From the natural abundance of these two isotopes, the intensity ratio is expected to be (CO 35 Cl) 2 :CO 35 ClCO 37 Cl:(CO 37 Cl) 2 ≈ 9:6:1. Therefore, the stronger peak at higher energy is assigned to (CO 35 Cl) 2 .…”

Section: Resultsmentioning

confidence: 97%

“…Here, we consider the direction of the phosphorescence polarization in oxalyl chloride. Although the rotational constants of oxalyl chloride are not experimentally determined, they are estimated to be A = 0.178, B = 0.049, and C = 0.039 cm -1 for (CO 35 Cl) 2 using the molecular parameters obtained in cryogenic rare gas matrices . This molecule is actually a prolate near-symmetric top molecule.…”

Section: Resultsmentioning

confidence: 99%

“…The band is assigned to a peak at 405 cm -1 , which is not clearly seen in Figure because of the weak intensity and overlap with a strong 400 cm -1 band. This 400 cm -1 band is assigned to by reference to the frequency in the ground state …”

Section: Resultsmentioning

confidence: 99%

See 4 more Smart Citations

Radiative and Nonradiative Processes in the Excited States of Jet-Cooled Oxalyl Chloride

et al. 1996

View full text Add to dashboard Cite

Phosphorescence and fluorescence excitation spectra of oxalyl chloride (COCl) 2 have been observed in a supersonic jet. Strong phosphorescence was observed for excitation of the 0 0 0 band of the T 1 3 A u (nπ*) r S 0 transition. From a vibrational analysis, it is shown that the molecule has C 2h symmetry in the T 1 excited state as well as in the S 0 ground state. Small splittings due to 35 Cl and 37 Cl isotopes were found in several vibronic bands. For the excitation of the S 1 0 0 0 band, phosphorescence with a short lifetime was observed, indicating fast intersystem crossing in the origin level. In the higher energy region, we could not observe phosphorescence but only weak fluorescence. It suggests existence of active nonradiative processes such as internal conversion and predissociation in the vibrationally excited levels of the S 1 state. A single-vibronic-level (SVL) dispersed phosphorescence spectrum has also been observed for the excitation of the T 1 CdO stretching band. The spectrum was dominated by bands at the same wavelengths as those for the 0 0 0 excitation. This clearly shows that intramolecular vibrational redistribution (IVR) takes place within the long triplet lifetime. Although oxalyl chloride is assumed to be a "small molecule", the radiationless transitions have been found to be efficient in both the T 1 and S 1 states.

show abstract