Analytic potentials and vibrational energies for Li2_{2} states dissociating to $\mbox{Li}\left(2S\right)+\mbox{Li}\left(3P\right)$. Part 1: The 2S+1Πu/g^{2S+1}Π_{u/g} states

preprint2015arXivOpen access

Abstract

Analytic potentials are built for all four 2S+1Πu/g^{2S+1}Π_{u/g} states of Li2_{2} dissociating to Li(2S)(2S) + Li(3P)(3P): 3b(33Πu)3b(3^{3}Π_{u}), 3B(31Πu)3B(3^{1}Π_{u}), 3C(31Πg),3C(3^{1}Π_{g}), and 3d(33Πg)3d(3^{3}Π_{g}). These potentials include the effect of spin-orbit coupling for large internuclear distances, and include state of the art long-range constants. This is the first successful demonstration of fully analytic diatomic potentials that capture features that are usually considered too difficult to capture without a point-wise potential, such as multiple minima, and shelves. Vibrational energies for each potential are presented for the isotopologues 6,6^{6,6}Li2_{2}, 6,7^{6,7}Li2_{2}, 7,7^{7,7}Li2_{2}, and the elusive `halo nucleonic molecule' 11,11^{11,11}Li2_{2}. These energies are claimed to be accurate enough for new high-precision experimental setups such as the one presented in {[}Sebastian \emph{et al.} Phys. Rev. A, \textbf{90}, 033417 (2014){]} to measure and assign energy levels of these electronic states, all of which have not yet been explored in the long-range region. Measuring energies in the long-range region of these electronic states may be significant for studying the \emph{ab initio} vs experiment discrepancy discussed in {[}Tang \emph{et al.} Phys. Rev. A, \textbf{84}, 052502 (2014){]} for the C3C_{3} long-range constant of Lithium, which has significance for improving the SI definition of the second.

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