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The ground-state energies and the radial and pair distribution functions of neutral 4He clusters are systematically calculated by the diffusion Monte Carlo method in steps of one 4He atom from 3 to 50...
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Measurement of the electronic transition dipole moment by Autler-Townes splitting: Comparison of three- and four-level excitation schemes for the Na2  A  1Sigma<sub>u</sub><sup>+</sup>–X  1Sigma<sub>g</sub><sup>+</sup> system

J. Chem. Phys. 124, 084308 (2006); doi:10.1063/1.2164454

Published 24 February 2006

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E. Ahmed, A. Hansson, P. Qi, T. Kirova, A. Lazoudis, S. Kotochigova, and A. M. Lyyra
Department of Physics, Temple University, Philadelphia, Pennsylvania 19122-6082

L. Li
Department of Physics and Key Laboratory of Atomic and Molecular Nanosciences, Tsinghua University, Beijing 100084, China

J. Qi
Department of Physics/Astronomy Penn State Berks, Tulpehocken Road, P.O. Box 7009, Reading, Pennsylvania 19610

S. Magnier
IUFM de Bretagne, 153 rue Saint Malo, CS 54310, F-35042 Rennes Cedex, France and Laboratoire de Physique des Atomes, Lasers, Molecules et Surfaces (PALMS), CNRS et Université Rennes 1 (UMR 6627), Campus de Beaulieu, Bâtiment 11B, F-35043 Rennes Cedex, France
We present a fundamentally new approach for measuring the transition dipole moment of molecular transitions, which combines the benefits of quantum interference effects, such as the Autler-Townes splitting, with the familiar R-centroid approximation. This method is superior to other experimental methods for determining the absolute value of the R-dependent electronic transition dipole moment function µe(R), since it requires only an accurate measurement of the coupling laser electric field amplitude and the determination of the Rabi frequency from an Autler-Townes split fluorescence spectral line. We illustrate this method by measuring the transition dipole moment matrix element for the Na2  A  1Sigma<sub>u</sub><sup>+</sup>  (v[prime]=25,  J[prime]=20e)-X  1Sigma<sub>g</sub><sup>+</sup>  (v[double-prime]=38,  J[double-prime]=21e) rovibronic transition and compare our experimental results with our ab initio calculations. We have compared the three-level (cascade) and four-level (extended Lambda) excitation schemes and found that the latter is preferable in this case for two reasons. First, this excitation scheme takes advantage of the fact that the coupling field lower level is outside the thermal population range. As a result vibrational levels with larger wave function amplitudes at the outer turning point of vibration lead to larger transition dipole moment matrix elements and Rabi frequencies than those accessible from the equilibrium internuclear distance of the thermal population distribution. Second, the coupling laser can be "tuned" to different rovibronic transitions in order to determine the internuclear distance dependence of the electronic transition dipole moment function in the region of the R-centroid of each coupling laser transition. Thus the internuclear distance dependence of the transition moment function µe(R) can be determined at several very different values of the R centroid. The measured transition dipole moment matrix element for the Na2  A  1Sigma<sub>u</sub><sup>+</sup>  (v[prime]=25,  J[prime]=20e)-X  1Sigma<sub>g</sub><sup>+</sup>  (v[double-prime]=38,  J[double-prime]=21e) transition is 5.5±0.2  D compared to our ab initio value of 5.9 D. By using the R-centroid approximation for this transition the corresponding experimental electronic transition dipole moment is 9.72 D at Rc=4.81  Å, in good agreement with our ab initio value of 10.55 D. ©2006 American Institute of Physics
History: Received 9 September 2005; accepted 13 December 2005; published 24 February 2006
Permalink: http://link.aip.org/link/?JCPSA6/124/084308/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.70.Ca
    Molecular oscillator and band strengths, lifetimes, transition moments, and Franck–Condon factors
  • 33.55.Be
    Zeeman and Stark effects (molecules)
  • 33.15.Kr
    Molecular electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility
  • 33.50.Dq
    Molecular fluorescence and phosphorescence spectra
  • 33.20.Vq
    Vibration-rotation analysis (molecular spectra)
  • 31.15.Ar
    Ab initio calculations (atoms and molecules)
  • YEAR: 2006

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