Theoretical Investigation of the Electronic Structure and Spectra of Mg(2+)He and Mg(+)He.

The ground and many excited states of the Mg(+)He van der Waals molecular system have been explored using a one-electron pseudopotential approach. In this approach, effective potentials are used to consider the Mg(2+) core and the electron-He effects. Furthermore, a core-core interaction is included. This has reduced the number of active electrons of the Mg(+)He, to be considered in the calculation, to a single valence electron. This has permitted to use extended Gaussian basis sets for Mg and He. Therefore, the potentianl energy and dipole moments calculations are carried out at the Hartree-Fock level of theory, and the spin-orbit effect is included using a semiclassical approach. The core-core interaction for the Mg(2+)He ground state is included using accurate CCSD(T) calculations. The spectroscopic constants of the Mg(+)He electronic states are extracted and compared with the existing theoretical works, where very good agreement is observed. Moreover, the transition dipole function has been determined for a large and dense grid of internuclear distances including the spin-orbit effect.

Electronic structure and spectra of the RbAr van der Waals system including spin-orbit interaction.

The potential energy curves and spectroscopic constants of the ground and excited states of the RbAr van der Waals system have been determined using a one-electron pseudopotential approach. This technique is used to replace the effect of the Rb(+) core and the electron-Ar interactions by effective potentials. The core-core interaction for Rb(+)Ar was incorporated using the accurate CCSD(T) potential of Hickling et al. [Hickling, H. L.; Viehland, L. A.; Shepherd, D. T.; Soldán, P.; Lee, E. P. F.; Wright, T. G. Phys. Chem. Chem. Phys. 2004, 6, 4233-4239]. This model reduces the number of active electrons of the RbAr van der Waals systems to just the single valence electron, permitting the use of very large basis sets for the Rb and Ar atoms. Using this approach, the potential energy curves of the ground and excited states dissociating into Rb(5s, 5p, 4d, 6s, 6p, 6d, and 7s) + Ar are calculated at the SCF level. Spin-orbit interaction was also considered within a semiempirical scheme for the states dissociating into Rb(5p) and Rb(6p). Spectroscopic constants are derived and compared with the available theoretical and experimental data. Such comparisons for RbAr show very good agreement for the ground and the first excited states. Furthermore, we have predicted the B(2)Σ(+)(1/2) ← X(2)Σ(+), A(2)Π(1/2) ← X(2)Σ(+), A(2)Π(3/2) ← X(2)Σ(+), A(2)Π(3/2) ← X(2)Σ(+), 5(2)Σ(+) ← X(2)Σ(+), 3(2)Π(1/2) ← X(2)Σ(+), and 3(2)Π(3/2) ← X(2)Σ(+) absorption spectra.

One-electron pseudopotential investigation of CsAr van der Waals system including the spin-orbit interaction.

The potential energy curves of the ground state and many excited states of the CsAr van der Waals system have been determined using [Cs(+)] and [Ar] core pseudopotentials and by considering core polarization operators on both atoms. This has permitted to reduce the number of active electrons of the CsAr system to only one electron, i.e., the valence electron, which led to use of large basis sets for Cs and Ar atoms. In this context, the potential energy curves of the ground state and many excited states are performed at the self consistent field (SCF) level. Spin-orbit interaction is also considered within a semiempirical scheme for the states dissociating into Cs(6p) and Cs(5d). The core-core interactions for Cs(+)Ar is included using the coupled cluster simple and double excitation (CCSD) accurate potential of Hickling et al. (Hickling, H.; Viehland, L.; Shepherd, D.; Soldan, P.; Lee, E.; Wright, T. Phys. Chem. Chem. Phys. 2004, 6, 4233). In addition, the spectroscopic constants of these states are derived and compared with the available theoretical and experimental works. Such comparison has shown a very good agreement for the ground and the first excited states. However, the spectroscopic data for the higher excited states are presented for the first time.