Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. After forming weakly bound molecules from atoms in cold collisions, the preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. Accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. This paper is dedicated to the vibrational analysis of potentially relevant electronically excited states in the alkali-metal (Li, Na, K, Rb)-alkaline-earth metal (Ca,Sr) diatomic series. Graphical maps of Frank-Condon overlap integrals are presented for all molecules of the group. By comparison to overlap graphics produced for idealized potential surfaces, we judge the usability of the selected states for future experiments on laser-enhanced molecular formation from mixtures of quantum degenerate gases.

We investigate the properties of alkali-alkaline earth diatomic molecules in the lowest Σ(+) states of the doublet and quartet multiplicity by ab initio calculations. In all sixteen cases studied, the permanent electric dipole moment points in opposite directions for the two spin states. This peculiarity can be explained by molecular orbital theory. We further discuss dissociation energies and bond distances. We analyze trends and provide an empirically motivated model for the prediction of the permanent electric dipole moment for combinations of alkali and alkaline earth atoms not studied in this work.

We report on the formation of mixed alkali–alkaline earth molecules (LiCa) on helium nanodroplets and present a comprehensive experimental and theoretical study of the ground and excited states of LiCa. Resonance enhanced multiphoton ionization time-of-flight (REMPI-TOF) spectroscopy and laser induced fluorescence (LIF) spectroscopy were used for the experimental investigation of LiCa from 15000 to 25500 cm–1. The 42Σ+ and 32Π states show a vibrational structure accompanied by distinct phonon wings, which allows us to determine molecular parameters as well as to study the interaction of the molecule with the helium droplet. Higher excited states (42Π, 52Σ+, 52Π, and 62Σ+) are not vibrationally resolved and vibronic transitions start to overlap. The experimental spectrum is well reproduced by high-level ab initio calculations. By using a multireference configuration interaction (MRCI) approach, we calculated the 19 lowest lying potential energy curves (PECs) of the LiCa molecule. On the basis of these calculations, we could identify previously unobserved transitions. Our results demonstrate that the helium droplet isolation approach is a powerful method for the characterization of tailor-made alkali–alkaline earth molecules. In this way, important contributions can be made to the search for optimal pathways toward the creation of ultracold alkali–alkaline earth ground state molecules from the corresponding atomic species. Furthermore, a test for PECs calculated by ab initio methods is provided.

Excited states and the ground state of the diatomic molecule RbSr were calculated by post Hartree-Fock molecular orbital theory up to 22 000 cm(-1). We applied a multireference configuration interaction calculation based on multiconfigurational self-consistent field wave functions. Both methods made use of effective core potentials and core polarization potentials. Potential energy curves, transition dipole moments, and permanent electric dipole moments were determined for RbSr and could be compared with other recent calculations. We found a good agreement with experimental spectra, which have been obtained recently by helium nanodroplet isolation spectroscopy. For the lowest two asymptotes (Rb (5s (2)S) + Sr (5s4d (3)P°) and Rb (5p (2)P°) + Sr (5s(2) (1)S)), which exhibit a significant spin-orbit coupling, we included relativistic effects by two approaches, one applying the Breit-Pauli Hamiltonian to the multireference configuration interaction wave functions, the other combining a spin-orbit Hamiltonian and multireference configuration interaction potential energy curves. Using the results for the relativistic potential energy curves that correspond to the Rb (5s (2)S) + Sr (5s4d (3)P°) asymptote, we have simulated dispersed fluorescence spectra as they were recently measured in our lab. The comparison with experimental data allows to benchmark both methods and demonstrate that spin-orbit coupling has to be included for the lowest states of RbSr.