Journal of the Chemical Society - Faraday Transactions p. 2671 - 2676 (1996)
Update date:2022-08-25
Topics:
Cooke, Stephen A.
Cotti, Gina
Hinds, Kelvin
Holloway, John H.
Legon
Lister, David G.
The ground-state rotational spectra of the three isotopomers 14N2...35ClF, 15N2...35ClF and 15N2...37ClF of a complex formed by dinitrogen and chlorine monofluoride have been observed with a pulsed-nozzle, Fourier-transform microwave spectrometer. The spectroscopic constants B0, DJ, χaa(A) (A) = 14Ni, 14No or Cl) and Mbb(Cl) are reported. The complex is shown to have a linear (or nearly linear) arrangement NoNi...ClF of the nuclei in the equilibrium conformation with r(Ni...Cl) = 2.920(2) A. The intermolecular stretching force constant, kσ = 5.00(5) N m-1, is implied by the centrifugal distortion constant DJ. Intepretation of the nuclear quadrupole coupling constants χaa(A) leads to the oscillation angles θav = cos-1〈cos2 θ〉1/2 = 17.8(5)° and φav = cos-1〈cos2 θ〉1/2 = 10(3)° for the N2 and ClF subunits, respectively. Additionally, the diffence χaa(Ni) - χaa(No) leads, on the basis of a simple model, to the conclusion that the polarisation of N2 attending complex formation is equivalent to the transfer of a fraction δ ≈ 0.02 of an electronic charge from No to Ni. A comparison of the properties of four related complexes N2...YF and OC...YF, where Y = Cl or H, is presented.
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