Rotational spectroscopy of newly detected atmospheric ozone depleters: CF 3 CH 2 Cl, CF 3 CCl 3, and CFClCCl 3 Zbigniew Kisiel, Ewa Białkowska-Jaworska,

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Rotational spectroscopy of newly detected atmospheric ozone depleters: CF 3 CH 2 Cl, CF 3 CCl 3, and CFClCCl 3 Zbigniew Kisiel, Ewa Białkowska-Jaworska, Lech Pszczółkowski, Institute of Physics, Polish Academy of Sciences, Warszawa, Poland Iciar Uriarte, Patricia Ecija, Francisco J. Basterretxea, Emilio J. Cocinero Departamento de Quimica Fisica, Universidad del Pais Vasco, (UPV-EHU), Bilbao, Spain 70th International Symposium on Molecular Spectroscopy RF11

Johannes C. Laube et al.,  Analysis of air samples from Tasmania + Analysis of air bubbles in Greenland snow  Four previously undetected ozone-depleting substances identified: CFC-112 = CFCl 2 CFCl 2 CFC-112a = CF 2 ClCCl 3 CFC-113a =CF 3 CCl 3 HCFC-133a =CF 3 CH 2 Cl  The concentrations of CFC-113a and HCFC-133a are increasing

Estimated emissions: CFC-11 = CFCl 3 Tasmanian air Greenland snow

Previous rotational spectroscopy: Current work:1/ chirped pulse and F-P cavity supersonic expansion FTMW 2/ broadband MMW up to 309 GHz CFC-112 = CFCl 2 CFCl 2  = 0 CFC-112a = CF 2 ClCCl 3  no previous work CFC-113a =CF 3 CCl 3  GHz Stark MMW Holm et al., Z.Naturforsch. 23a, 1040 (1968) Carpenter et al., J.Mol.Spectrosc. 154, 207 (1992) Seo et al., J.Mol.Spectrosc. 169, 58 (1995) HCFC-133a =CF 3 CH 2 Cl  8-26 GHz Stark Ogata et al., J.Mol.Struct. 144, 1 (1986)

CF 3 CH 2 35 Cl in the chirped pulse spectrum: 3 22     4 14 Fits made with SPFIT/SPCAT + AABS used as the graphical front end fitted data points HCFC-133a

Chirped-pulse sensitivity: CF 3 CCH 2 37 Cl 3 12  2 11, F = 3/2  3/2 (weak a R-type transition) 13 C + 37 Cl species assigned in natural abundance HCFC-133a fitted data points

The MMW spectrum of CF 3 CH 2 Cl: cavity FTMW v=0:  fit 1.8 kHz chirped-pulsev=1: 3.6 kHz MMWv=2:37.1 kHz GLOBAL FIT: N trans 2235  rms HCFC-133a

Key results for Key results for CF 3 CH 2 Cl:  Rotational, centrifugal distortion, and chlorine hyperfine splitting constants for 6 isotopic species HCFC-133a  The off-diagonal hyperfine constant determined precisely:  ab =52.105(14) MHz for CF 3 CH 2 35 Cl, leading to useful angular information: See the discussion of structural and hyperfine angles in: J.Chem.Phys. 109, (1998)

Chlorine hyperfine structure in CF 3 C 35 Cl 3 : CFC-113a J = 4  3 J = 2  1 Cavity FTMW preferred due to better resolution.

Hyperfine splitting structure in the 1  37 Cl species: CFC-113a J = 3  2 K=0 components highlighted Comparison of the spectrum and the final fit

Global fits of cavity FTMW and MMW data: CFC-113a 1  37 Cl species 3  35 Cl species Using program PIFORM from the website Using program PIFORM from the PROSPE website K = CF 3 C 35 Cl 3

The A constant in CF 3 C 35 Cl 3 from hyperfine analysis: CFC-113a previous estimate:A = 1290 MHz Current global fit:A = (16) MHz (symmetric top) From B3LYP/6-311G++(d,p) A = MHz geometry rescaled to 1  37 Cl species Global fit for 1  37 Cl species:A = (38) B = (5) C = (4) Using P a,P b,P c scaling in program CORSCL from the website Using P a,P b,P c scaling in program CORSCL from the PROSPE website

The chirped-pulse rotational spectrum of CF 2 ClCCl 3 : Cl 2 Cl 1 Cl 3 parent 5 51   4 41 transition region A,B,C determined CFC-112a 

Hyperfine structure (4 chlorine nuclei): Using symmetric top quantisation to fit in 6 quantum numbers 64-bit compilation of SPFIT/SPCAT mandatory and executables for Windows and Linux are now available on the PROSPE website. CFC-112a

 Rotational spectroscopy on HCFC-133a and CFC-113a considerably updated using several contemporary experimental techniques  The triple chlorine hyperfine structure for symmetric and asymmetric species of CFC-113a analysed including determination of the A rotational constant in the parent symmetric-top species enabled by hyperfine-mediated perturbations  The rotational spectrum of CFC-112a assigned using chirped-pulse FTMW  The hyperfine information for CF 3 CCl 3 allows interesting comparisons with that for related triple-chlorine molecules: CHCl 3, CH 3 CCl 3, and CNCCl 3  The hyperfine structure of CFC-112a still needs to be analysed… CONCLUSIONS: