THE $A {^{1}}\Sigma^{+}_{u}$ STATE OF $^{7}Li_{2}$ FROM 2 TO 102 {\AA}

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2002

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Ohio State University

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The A1Σu+ state of 7Li2 has been observed in several types of experiment: absorption, laser induced fluorescence, stimulated emission pumping. We recorded the absorption spectrum on a Fourier transform spectrometer using a heatpipe source; Doppler-limited linewidths were about 0.1cm−1. This experiment probed vibrational levels 0-20 and rotational levels 0-60. A selection of A-X laser-induced fluorescence spectra was also recorded, exciting v≤5 in the A state; they describe the X1Σg+ ground state up to v=10. We used optical-optical double resonance excitation to excite the E or F1Σg+ states, and recorded FA and EA infrared fluorescence (0≤v≤87,16≤J≤26) again by FT spectrometry. The SEP experiment probed the A state through all-optical triple resonance, using GAX excitation.a Rotational levels 2≤J≤22 were probed at high resolution for 27≤v≤62, and calibrated against the iodine atlas. Data reduction led to a set of 1385 rovibrational energies in the A state, which were fitted to a numerical potential energy curve. A photoassociation experiment performed at Rice Universityb furnishes accurate binding energies with respect to the Li(2s)+Li(2p)2Pi1/2 asymptote for J≤2 in levels 65≤v≤97. Because several vibrational levels were observed both in photoassociation and in fluorescence, an experimental dissociation energy can be deduced from the sum of binding energies (measured in photoassociation) and vibrational energies established with respect to the potential minimum (from fluorescence data), giving De=9352.16±0.02cm−1. This value can be compared with the value obtained for the A state of 6Li2,De=9352.032±0.008cm−1 to reveal a very small non Born-Oppenheimer contribution to the molecular potential. The full set of energies can be reproduced from a numerical potential curve extending beyond 100 {\AA}.

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aK. Urbanski, S. Antonova, A. Yiannopoulou, A. M. Lyyra, Li Li and W. C. Stwalley, J. Chem. Phys. 104 2813 (1996) bE. Abraham, N. Ritchie, W. McAlexander and R. Hulet, J. Chem. Phys. 103 7773 (1995)


Author Institution: Laboratoire de Spectrom'{e}trie Ionique et Mol'{e}culaire (UMR 5579 CNRS), B^{a}timent Kastler, Universit'{e} Lyon I, Domaine Scientifique de la Doua; Department of Physics, Temple University; Physics Department, University of New Brunswick

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