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Issue 15, 2008
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Pure rotational spectra of PbSe and PbTe: potential function, Born–Oppenheimer breakdown, field shift effect and magnetic shielding

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Abstract

The pure rotational spectra of 41 isotopic species of PbSe and PbTe have been measured in their X 1Σ+ electronic state with a resonator pulsed-jet Fourier transform microwave spectrometer. The molecules were prepared by laser ablation of suitable target rods and stabilised in supersonic jets of noble gas. Global multi-isotopologue analyses yielded spectroscopic Dunham parameters Y01, Y11, Y21, Y31, Y02, and Y12 for both species, as well as effective Born–Oppenheimer breakdown (BOB) coefficients δ01 for Pb, Se and Te. Unusual large values of the BOB parameters for Pb have been rationalized in terms of finite nuclear size (field shift) effect. A direct fit of the same data sets to an appropriate radial Hamiltonian yielded analytic potential energy functions and BOB radial functions for the X 1Σ+ electronic state of both PbSe and PbTe. Additionally, the magnetic hyperfine interactions produced by the uneven mass number A nuclei 207Pb, 77Se, 123Te, and 125Te were observed, yielding first determinations of the corresponding nuclear spin–rotation coupling constants.

Graphical abstract: Pure rotational spectra of PbSe and PbTe: potential function, Born–Oppenheimer breakdown, field shift effect and magnetic shielding

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Publication details

The article was received on 01 Nov 2007, accepted on 14 Jan 2008 and first published on 20 Feb 2008


Article type: Paper
DOI: 10.1039/B716896A
Citation: Phys. Chem. Chem. Phys., 2008,10, 2078-2088
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    Pure rotational spectra of PbSe and PbTe: potential function, Born–Oppenheimer breakdown, field shift effect and magnetic shielding

    B. M. Giuliano, L. Bizzocchi, S. Cooke, D. Banser, M. Hess, J. Fritzsche and J. Grabow, Phys. Chem. Chem. Phys., 2008, 10, 2078
    DOI: 10.1039/B716896A

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