Electron Spin Resonance Spectra of ClCO and ClOO

We have observed the electron spin resonance (ESR) spectra of ClCO and ClOO trapped in polycrystalline CO and Ar, respectively, at 4°K. The radicals were prepared by reaction of a Cl atom, produced by photolytic decomposition of Cl2, with CO and O2. The ESR spectra of these radicals are complicated by, among other things, the Cl nuclear quadrupole interaction. For ClCO the g factor tensor is gz = 1.9980, gx = 2.0061, gy = 2.0003; the hyperfine splitting (hfs) tensor is Az = 227, Ax = 58, Ay = 50 MHz; and the nuclear quadrupole coupling constants are e2Qq = 76 MHz and η = 0.25. For ClOO these spin Hamiltonian parameters are: gz = 2.0100, gx = 1.9987, gy = 1.9915  ; | Az | = 50, | Ax | = 9, | Ay | = 16 MHz; and e2Qq = 105 MHz. The z principal axis is along the Cl bond, and the x principal axis is perpendicular to the molecular plane. The signs of the hfs tensor components of ClCO were assigned in accordance with previous results for FCO. This assignment led to a value of 0.42 for the unpaired electron densi...

[1]  E. Schempp,et al.  Nuclear Quadrupole Coupling Constants , 1969 .

[2]  F. Adrian.  Guidelines for interpreting electron spin resonance spectra of paramagnetic species adsorbed on surfaces , 1968 .

[3]  F. Adrian.  ESR Spectrum and Structure of O2F , 1967 .

[4]  E. Cochran,et al.  13C Hyperfine Splittings in the Electron Spin Resonance Spectra of HCO and FCO , 1966 .

[5]  D. E. Milligan,et al.  Matrix Isolation Study of the Reaction of Cl Atoms with CO. The Infrared Spectrum of the Free Radical ClCO , 1965 .

[6]  E. Cochran,et al.  Electron Spin Resonance Spectrum of FCO , 1965 .

[7]  D. E. Mann,et al.  Matrix-isolation study of the reaction of f atoms with co - infrared and ultraviolet spectra of the free radical fco. , 1965 .

[8]  J. Maruani,et al.  Use of Computer Programs in the Interpretation of Electron Paramagnetic Resonance Spectra of Dilute Radicals in Amorphous Solid Samples. I. High‐Field Treatment. X‐Band Spectra of π‐Electron Unconjugated Hydrocarbon Radicals , 1965 .

[9]  H. Kashiwagi,et al.  Pure quadrupole resonance of halogens in compounds containing a nitrogenhalogen bond , 1965 .

[10]  J. Morton.  ELECTRON SPIN RESONANCE SPECTRA OF ORIENTED RADICALS , 1964 .

[11]  E. Cochran,et al.  ESR Study of Ethynyl and Vinyl Free Radicals , 1964 .

[12]  E. Cochran,et al.  ESR Spectrum and Structure of the Formyl Radical , 1962 .

[13]  E. Cochran,et al.  Anisotropic Hyperfine Interactions in the ESR Spectra of Alkyl Radicals , 1961 .

[14]  R. E. Robertson,et al.  Spectroscopic splitting factors in aromatic radicals , 1957 .

[15]  C. Townes,et al.  The Ionic Character of Diatomic Molecules , 1955 .

[16]  R. Bersohn.  Double‐Bond Character of Conjugated Carbon‐Chlorine Bonds , 1954 .

[17]  G. W. Robinson,et al.  The Microwave Spectrum of Phosgene , 1953 .

[18]  L. Pauling.  The Nature Of The Chemical Bond , 1939 .