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Non-adiabatic mass-correction functions and rovibrational states of 4 He 2 + ( X 2 Σ u + ).
Journal of Chemical Physics 2018 November 22
The mass-correction functions in the second-order non-adiabatic Hamiltonian are computed for the 4 He 2 + molecular ion using the variational method, floating explicitly correlated Gaussian functions, and a general coordinate-transformation formalism. When non-adiabatic rovibrational energy levels are computed using these (coordinate-dependent) mass-correction functions and a highly accurate potential energy and diagonal Born-Oppenheimer correction curve, significantly improved theoretical results are obtained for the nine rotational and two rovibrational intervals known from high-resolution spectroscopy experiments.
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