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Long-range interaction of the 39K(4s)+39K(4p) asymptote by photoassociative spectroscopy. I. The 0<sub>g</sub><sup>-</sup> pure long-range state and the long-range potential constants

J. Chem. Phys. 106, 7899 (1997); doi:10.1063/1.473804

Issue Date: 15 May 1997

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H. Wang, P. L. Gould, and W. C. Stwalley
Department of Physics, U-46, University of Connecticut, Storrs, Connecticut 06269
This paper reports on a comprehensive study of the long-range interaction of the 39K(4s)+39K(4p) asymptotic system. We present a detailed discussion of the R-dependent angular momentum couplings and correlation between the Hund's case (a) and case (c) molecular states. Analytical expressions for the 16 adiabatic Hund's case (c) long-range potential curves are derived including the higher order dispersion forces and the effects of retardation. Experimentally, six Hund's case (c) long-range molecular states (0<sub>u</sub><sup>+</sup>, 1g, and 0<sub>g</sub><sup>-</sup> dissociating to the 4 2S1/2+4 2P3/2 asymptote and 0<sub>u</sub><sup>+</sup>, 1g, and 0<sub>g</sub><sup>-</sup> to the 4 2S1/2+4 2P1/2 limit) are observed with rovibrational resolution by photoassociative spectroscopy of ultracold 39K atoms in a high density magneto-optical trap (MOT). Among the six observed long-range states, the upper 0<sub>g</sub><sup>-</sup> "pure long-range" state has negligible short-range chemical exchange contributions and the measured molecular binding energies (v=0–26) are used to precisely determine the long-range potential constants of the 4s+4p interaction. We determine: C<sub>3</sub><sup>Pi</sup>=8.436(14) a.u., C<sub>3</sub><sup>Sigma</sup>=16.872(28) a.u., C<sub>6</sub><sup>Pi</sup>=6272(94) a.u., and C<sub>6</sub><sup>Sigma</sup>=9365(141) a.u.. Molecular constants for the three special pure long-range states, the 0<sub>g</sub><sup>-</sup> and 1u (dissociating to the 4 2P3/2 limit and with potential minimum) and the 1u (dissociating to the 4 2P1/2 and with potential maximum), are reported. The internal consistency of the theoretical model used in this work is confirmed by the excellent agreement between the long-range potential curve of the 1g state obtained in present work (from the 0<sub>g</sub><sup>-</sup> state) and the long-range portion of the RKR potential curve of the 1 1Pig state previously determined by conventional molecular spectroscopy. The radiative lifetime of the K 4p state derived from the dipole–dipole interaction constant C<sub>3</sub><sup>Pi</sup> is also in excellent agreement with a recent fast-beam measurement. ©1997 American Institute of Physics.
History: Received 12 December 1996; accepted 10 February 1997
Permalink: http://link.aip.org/link/?JCPSA6/106/7899/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.30.Nr
    Physical Chemistry Specific chemical reactions; reaction mechanisms Association, addition, insertion, cluster formation, hydrogen bonding
  • 82.20.Kh
    Physical Chemistry Chemical kinetics Potential energy surfaces for chemical reactions
  • 34.20.Mq
    Atomic and molecular collision processes and interactions Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions Potential energy surfaces for collisions
  • 82.50.-m
    Physical Chemistry Photochemistry and radiation chemistry
  • 34.20.Cf
    Atomic and molecular collision processes and interactions Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions Interatomic potentials and forces
  • 33.15.Ry
    Molecular properties and interactions with photons Properties of molecules and molecular ions Ionization potentials, electron affinities, molecular core binding energy
  • 33.20.Vq
    Molecular properties and interactions with photons Molecular spectra Vibrationrotation analysis
  • 33.15.Mt
    Molecular properties and interactions with photons Properties of molecules and molecular ions Rotation, vibration, and vibrationrotation constants
  • 82.30.Cf
    Physical Chemistry Specific chemical reactions; reaction mechanisms Atom and radical reactions; chain reactions
  • 32.70.Cs
    Atomic properties and interactions with photons Intensities and shapes of atomic spectral lines Oscillator strengths, lifetimes, transition moments
  • YEAR: 1996-97

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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