Possible sources of residual errors in the theoretical energies of the hydrogen molecule are investigated. Nonadiabatic corrections are computed for all bound, J≤10 X 1Σg+ ro‐vibrational states of the six isotopic hydrogen molecules. The new results improve significantly the overall agreement with accurate experimental transition frequencies. In order to estimate the convergence errors of the Born–Oppenheimer energies generalized James–Coolidge functions with powers of the interelectronic distance, r12, up to 6 are used and the precision of the computations is increased. Except for the equilibrium separation, R=1.4011 bohr, the obtained potential energy curve is lower by a few thousandths of a wave number than any other reported variational result. This lowers the v=0 vibrational levels by 0.009 cm−1 and results in a dissociation energy of H2, D0=36118.069 cm−1.
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Research Article| August 01 1995
Nonadiabatic energies of the ground state of the hydrogen molecule
L. Wolniewicz; Nonadiabatic energies of the ground state of the hydrogen molecule. J. Chem. Phys. 1 August 1995; 103 (5): 1792–1799. https://doi.org/10.1063/1.469753
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