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摘要
We theoretically study 37 Rydberg states of HeH derivable from the He(1s(2)) + H(nl) configuration with n 5 along with three states with n = 6. The multireference configuration interaction method is used to calculate their electronic energy curves (EECs) for the internuclear distance R from 0 to 28a(0), which are regarded as the united-atom (UA) and separated-atoms (SA) limits, respectively. The 15 Rydberg series (ns sigma, np sigma, nd sigma, nf sigma, ng sigma, nd, nf, ng, ng, np, nd, nf, ng, nf phi, and ng phi) are identified. Bingel's perturbation theory is used to explain the role of the core part and the Rydberg orbitals in the behavior of EECs at small R. Smith's theory of diabatization is directly solved to obtain the diabatic quantum defect curves (QDCs). From the correlations in diabatic QDCs between the UA and SA limits, the following order of orbital energies in the equilibrium region is found: np sigma < ns sigma < np < nd sigma < nd < nf sigma < nf < nf < nf phi < nd, except 5d < 5f phi. This order is identical to that in one-electron molecular systems at small R, except for the ns sigma and np series. The correlation rules are n(UA) = n(SA) + 1 for the np sigma series and n(UA) = n(SA) for other series; additionally, l(UA) = l(SA) for all cases except for the 2p sigma - sigma 1s correlation. A reversal of the diabatic dipole moment at avoided crossing points of the ns sigma and np sigma series is observed, and explained by the behaviors of ns and np wavefunctions of H at small R.
- 出版日期2016-4
