We compare the explicitly correlated Hylleraas and exponential basis sets in the evaluations of ground state of Li and Be + . Calculations with Hylleraas functions are numerically stable and can be performed with the large number of basis functions. Our results for ground state energies −7.478 060 323 910 10(32), −14.324 763 176 790 43(22) of Li and Be + correspondingly, are the most accurate to date. When small basis set is considered, explicitly correlated exponential functions are much more effective. With only 128functions we obtained about 10 −9 relative accuracy, but the severe numerical instabilities make this basis costly in the evaluation.

We model the binding energies of rovibrational levels of the RbYb molecule using experimental data from two-color photoassociation spectroscopy in mixtures of ultracold 87 Rb with various Yb isotopes. The model uses a theoretical potential based on state-of-the-art ab initio potentials, further improved by least-squares fitting to the experimental data. We have fixed the number of bound states supported by the potential curve, so that the model is mass scaled, that is, it accurately describes the bound state energies for all measured isotopic combinations. Such a model enables an accurate prediction of the s-wave scattering lengths of all isotopic combinations of the RbYb system. The reduced mass range is broad enough to cover the full scattering lengths range from −∞ to +∞. For example, the 87 Rb 174 Yb system is characterized by a large positive scattering length of +880 (120) Yb. Hyperfine corrections to these scattering lengths are also given. We further complement the fitted potential with interaction parameters calculated from alternative methods. The recommended value of the van der Waals coefficient is C 6 =2837(13) a.u. and is in agreement and more precise than the current state-of-the-art theoretical predictions (S. G. Porsev, M. S. Safronova, A. Derevianko, and C.W. Clark, arXiv:1307.2654).

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Variational calculations employing explicitly correlated Gaussian functions and explicitly including the nuclear motion [i.e., without assuming the Born-Oppenheimer (BO) approximation] have been performed to determine the lowest singlet transition energy in the 9Be atom. The non-BO wave functions were used to calculate the alpha2 relativistic corrections (alpha=1/137.035,999,679). With those corrections and with the alpha3 and alpha4 QED corrections determined previously by others, we obtained 54,677.35 cm(-1) for the 3(1)S-->2(1)S transition energy. This result falls within the error bracket for the experimental transition of 54,677.26(10) cm(-1). This is the first time an electronic transition of Be has been calculated from first principles with the experimental accuracy.

Different generalized Douglas-Kroll transformed Hamiltonians (DKn, n=1, 2,...,5) proposed recently by Hess et al. are investigated with respect to their performance in calculations of the spin-orbit splittings. The results are compared with those obtained in the exact infinite-order two-component (IOTC) formalism which is fully equivalent to the four-component Dirac approach. This is a comprehensive investigation of the ability of approximate DKn methods to correctly predict the spin-orbit splittings. On comparing the DKn results with the IOTC (Dirac) data one finds that the calculated spin-orbit splittings are systematically improved with the increasing order of the DK approximation. However, even the highest-order approximate two-component DK5 scheme shows certain deficiencies with respect to the treatment of the spin-orbit coupling terms in very heavy systems. The meaning of the removal of the spin-dependent terms in the so-called spin-free (scalar) relativistic methods for many-electron systems is discussed and a computational investigation of the performance of the spin-free DKn and IOTC methods for many-electron Hamiltonians is carried out. It is argued that the spin-free IOTC rather than the Dirac-Coulomb results give the appropriate reference for other spin-free schemes which are based on approximate two-component Hamiltonians. This is illustrated by calculations of spin-free DKn and IOTC total energies, r(-1) expectation values, ionization potentials, and electron affinities of heavy atomic systems.