Raman, infrared and ultraviolet spectra of the chlorine difluoride free radical in solid nitrogen

Prochaska, Eleanor S.; Andrews, Lester

doi:10.1021/ic50168a023

Cited by 20 publications

(6 citation statements)

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“…CIF2 and C13, have been experimentally characterized . The former of these is found to have [7] a symmetric bent structure and the latter to have [8] a slightly asymmetric linear structure in the ground state. Ab initio SCF calculations of Ungemach and Schaefer [2] support the experimental structure of ClF2, but no such theoretical study has yet been made to substantiate the observed structure of c13.…”

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confidence: 99%

“…However, for the present systems the predictions that the asymmetric conformers are more stable than the symmetric ones is possibly wrong. From the mutual exclusion of some Raman-and IR-active lines in CIF2, Prochaska and Andrews [7] concluded that this radical might have symmetric linear structure. However, their final conclusion is that CIF2 is a symmetric bent molecule.…”

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Electronic structure of triatomic interhalogens

Sannigrahi

1982

Int J of Quantum Chemistry

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Although a number of trihalide ions have long been experimentally characterized [I], very little is known about the parent neutral radicals. Available experimental [ 11 and ab initio theoretical [2,3] Ungemach and Schaefer [2] support the experimental structure of ClF2, but no such theoretical study has yet been made to substantiate the observed structure of c13. The CND0/2 (spd) calculations of Vasini and Castro [9] on C I S and CI3 indicate that both the radicals possess a linear symmetric structure. In view of the fact that they obtained very irregular angular potential (AP) curves (the AP curve of C I S shows a minimum at 100' and constant energy in the range of 17Oo-18O0, whereas the AP curve of C13 shows minima at looo, 160°, and 180') and performed the SCF iterations on C13 with a precision of hartree, their conclusion is very much questionable. Deb et al.[ID] also performed CND0/2 (spd) calculations on CIF2 and predicted a linear symmetric structure. It is, however, well known [l 11 that CND0/2 (spd) calculations with original parameters [12] overestimate the bond angles and underestimate the bond lengths. We therefore carried out CND0/2 and INDO calculations [13] on CIF2 and c 1 3 using sp basis set, and observed that both of them possess symmetric bent structure. In order to obtain more information about the structural pattern of triatomic interhalogens in general, we have performed similar calculations on four additional systems, namely, F3, FFCl (the asymmetric conformer of CIFz), ClFCl (the symmetric conformer of CIzF), and ClClF (the asymmetric conformer of C12F). Since it is not convenient to discuss molecular electronic structure on the basis of composition and population of the occupied MO' s obtained from UHF-type calculations, we have also performed RHF-type calculations on some of the molecule.For the UHF calculations we have followed the same method of calculations as outlined in our previous paper [I 31. The RHF The calculated ground state geometry of F3, FCIF, FFCI, CIFCI, CICIF, and CI3 is given in Table I along with the available experimental and ab initio theoretical values. We carried out RHF calculations only for FCIF, ClFC1, and C13 since we thought that the results of these calculations might be considered as representative of the entire series. Considering the equilibrium geometrical parameters in Table I we find that with the exception of CIFCI, all the molecules are predicted to have a bent structure. The RHF calculations yield somewhat smaller interbond angles for the bent molecules than the corresponding UHF calculations. A similar trend isbbserved when the results of CND0/2 and INDO calculations are compared. As regards

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confidence: 99%

Electronic structure of triatomic interhalogens

Sannigrahi

1982

Int J of Quantum Chemistry

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“…Mamantov and co-workers [50] first reported the stabilization of the previously unobserved twenty-one valence electron molecule CIF 2 in matrix isolation studies of the photolysis of F 2 in the presence of CIF. Subsequent nitrogen-matrix infrared and Raman studies by Prochaska and Andrews [51] confirmed the conclusion that ClF 2 is bent, with a valence angle of 136 ± 4 °.…”

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confidence: 84%

Spectroscopy and photochemistry of free radicals formed by the reaction of F atoms with small molecules

Jacox

1985

Res Chem Intermed

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“…Fluorine containing trihalogens were observed and characterized in rare gas matrices using infrared ͑IR͒ absorption and Raman spectroscopy. [9][10][11][12][13] Hutton and Wright 3 proposed a formation mechanism of trichloride radical Cl 3 from Cl atom recombination in the presence of Cl 2 , Cl + Cl 2 + M → Cl 3 + M , ͑1a͒…”

Section: Introductionmentioning

confidence: 99%

Direct observation and reactions of Cl3 radical

Enami

Yamanaka

Hashimoto

et al. 2006

The Journal of Chemical Physics

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The broad absorption of Cl 3 radical was observed between 1150 and 1350 nm using cavity ring-down spectroscopy at 213-265 K and 50-200 Torr with He, N 2 , Ar, or SF 6 diluents. The absorption intensity of Cl 3 increased at lower temperature and higher pressure. SF 6 was the most efficient diluent gas. The temperature dependent equilibrium constants for Cl 3 formation from Cl+ Cl 2 were theoretically calculated at the MP4SDQ/ 6-311+ G͑d͒ level. Observed decay time profiles of Cl 3 and the pressure dependence of Cl 3 formation are explained by the equilibrium reaction and a decay reaction of Cl+ Cl 3 .

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Raman, infrared and ultraviolet spectra of the chlorine difluoride free radical in solid nitrogen

Cited by 20 publications

References 21 publications

Electronic structure of triatomic interhalogens

Electronic structure of triatomic interhalogens

Spectroscopy and photochemistry of free radicals formed by the reaction of F atoms with small molecules

Direct observation and reactions of Cl3 radical

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