Raman spectra of Cl and Br at 12 K produced from the reaction of HCl or HBr with NO₂

Abstract

ClN03, NO;, NO,, and sym-NzOz was found. For the reaction with HBr only Br: was detected due to resonance Raman enhancement effects. These results are consistent with the previously proposed gas-phase reaction scheme for HCI+NOz. However, the reaction proceeds further at low temperatures to produce Cl: (or Br;). The Raman frequencies for Cl: were observed at 515(v3), 462(v1), and 236cm-'(uz). The BrS resonance Raman spectra, which represent the first well documented spectra for this species, show strong fundamental bands at 281(vl) and 227 and 238 cm-' (doublet for v,) as well as an overtone doublet at 471 and 487 Em-'.

Gaseous Cl3+ and Cl2F+ cations. a joint mass spectrometric and theoretical study

“…Passing to Cl 2 F , the present calculations confirm that the asymmetric bent singlet III is the global minimum, being more stable than the symmetric singlet IV by 43.9 kcal mol À1 at 298 K. Based on the DH°1 2 change (Table 1), H°f (Cl 2 F ) amounts to 245.0 kcal mol À1 and the BE of Cl to ClF, 71.0 kcal mol À1 , is lower than to Cl 2 , consistent with the occurrence of Cl transfer, see (5). As a final remark, whenever comparable, the present computational results are in good general agreement with those of previous studies.…”

“…2 This paper reports the preparation and characterization, by mass spectrometric and theoretical methods, of gaseous Cl 3 and Cl 2 F cations, long known in the solid AsF 6 À salts. 3,4,5 Cl 3 ions (1) were prepared by two alternative routes in the external chemical ionization (CI) source of a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer and unambiguously identified from accurate mass measurements. The former route utilizes Cl 2 H , obtained by methane CI of Cl 2 , 6 that promotes the reaction Cl 2 H Cl 2 À31 HCl 1 where 1 denotes Cl 3 .…”

Silver Complexes of Dihalogen Molecules

“…The terminal ν ( X ‐ X ) stretches are among the highest ever recorded and suggest decoupling of the ν ( X ‐ X ) mode from admixtures of bands including the silver atom. They are similar to Cl 3 + (515 cm −1 ), Br 5 + (309 cm −1 ) and I 5 + (207 cm −1 ) as well as Ag(I 2 )SbF 6 (208 cm −1 ) …”

Homopolyatomic and heteropolyatomic halogen cations

“…The homopolyatomic cations Br2+ [13,14,Br3+ [14,15,27,and Brs+ [14,15] have been well characterized. Whereas the Br2' cation has been known for many years, both in form of its Sb3F16-salt and in superacid solutions, it was not until 1991 that the structures of Br3+ (X-ray) and Brs+ (X-ray) were elucidated [14,16].…”