Theoretical calculations for the ground state and for 83 excited states of the Na2 molecule are presented in the framework of two independent approaches. The electron–core interaction is represented either by a pseudopotential or by a model potential, and a core polarization potential is introduced in both cases. The basis set contains either Gaussian orbitals or two‐center generalized Slater orbitals. The two methods appear to give similar results, one being more accurate for the ground and first excited states, the other being better adapted to the intermediate Rydberg states. A very good agreement is obtained with the experimental spectroscopic constants determined for 26 states, the mean deviation being ΔRe=0.05a0, Δωe=0.86 cm−1, and ΔDe=57 cm−1.

Potential curves for the ground and excited states of the Na2 molecule up to the (3s+5p) dissociation limit: Results of two different effective potential calculations

The rapid development of experimental techniques to produce ultracold alkali molecules opens the ways to manipulate them and to control their dynamics using external electric fields. A prerequisite quantity for such studies is the knowledge of their static dipole polarizability. In this paper, we computed the variations with internuclear distance and with vibrational index of the static dipole polarizability components of all homonuclear alkali dimers including Fr2, and of all heteronuclear alkali dimers involving Li to Cs, in their electronic ground state and in their lowest triplet state. We use the same quantum chemistry approach as in our work on dipole moments [Aymar and Dulieu, J. Chem. Phys. 122, 204302 (2005)], based on pseudopotentials for atomic core representation, Gaussian basis sets, and effective potentials for core polarization. Polarizabilities are extracted from electronic energies using the finite-field method. For the heaviest species Rb2, Cs2, and Fr2 and for all heteronuclear alkali d...

Calculations of static dipole polarizabilities of alkali dimers: prospects for alignment of ultracold molecules.

Core-valence basis sets for the alkali and alkaline earth metals Li, Be, Na, Mg, K, and Ca are proposed. The basis sets are validated by calculating spectroscopic constants of a variety of diatomic molecules involving these elements. Neglect of (3s, 3p) correlation in K and Ca compounds will lead to erratic results at best, and chemically nonsensical ones if chalcogens or halogens are present. The addition of low-exponent p functions to the K and Ca basis sets is essential for the smooth convergence of molecular properties. Inclusion of inner-shell correlation is important for accurate spectroscopic constants and binding energies of all the compounds. In basis set extrapolation/convergence calculations, the explicit inclusion of alkali and alkaline earth metal subvalence correlation at all steps is essential for K and Ca, strongly recommended for Na, and optional for Li and Mg, while in Be compounds an additive treatment in a separate ‘core correlation’ step is probably sufficient. Consideration of (ls) i...

Alkali and alkaline earth metal compounds: core-valence basis sets and importance of subvalence correlation

We report the experimental observation of electromagnetically induced transparency (EIT) in an inhomogeneously broadened V-type Na2 molecular system. The experiment is performed with both co- and counterpropagating arrangements for the propagation directions of the coupling and probe laser beams. In our theoretical model we employ the density matrix formalism, as well as perturbative methods for obtaining the probe field absorption profile for both open and closed systems. Simulations of the experimental data show excellent agreement with the predictions derived from the basic theory. Our fluorescent intensity measurements show that, in the copropagating configuration, the EIT plus saturation window depth is about 95%, while under similar conditions in the counterpropagating geometry we observed 40%‐45% reduction in the fluorescence signal around the line center. To separate the two simultaneously occurring mechanisms in a V-type system (i.e., EIT and saturation) that are induced by the coupling field, we have carried out theoretical calculations which show that, in the copropagating case, a significant fraction of the depth of the dip is due to the coherent effect of EIT. When the coupling and probe beams are in the counterpropagating configuration, the dip is mostly due to saturation effects alone.

/pdf/electromagnetically-induced-transparency-in-an-open-v-type-3qsp39tb3m.pdf

Electromagnetically induced transparency in an open V-type molecular system

Current spectroscopic data on dimers (molecules consisting of two similar atoms) and their ions are presented and analysed. Methods for obtaining such data are discussed.

Properties of dimers

The laser-induced fluorescence of the and transitions of Na2 are analysed, using high resolution Fourier transform spectroscopy. Fixed-frequency ion-laser lines (4880 and 4765 A (1 A = 10−10 m) from Ar+ and 6471 and 4762 A from Kr+) together with laser frequencies from a ring dye laser, using rhodamine 6 G with λ = 5781.22 and 5796.80 A, were used to excite Na dimer in the gas phase. Twenty-eight series of and systems have been assigned and analysed, and the strong transitions are accompanied by numerous rotational relaxation lines. Molecular constants of the state were calculated with high precision from simultaneous least-squares fits to 1410 lines assigned to the A–X and B–X systems. These constants have been used to determine the Rydberg–Klein–Rees potential curve of the X ground state for vibrational levels up to ν = 62.

K. Hussein

Papers

The ground state of Na2