All-electron and relativistic pseudopotential studies for the group 1 element polarizabilities from K to element 119

Lim, Ivan S.; Schwerdtfeger, Peter; Metz, Bernhard; Stoll, Hermann

doi:10.1063/1.1856451

Cited by 296 publications

(263 citation statements)

References 47 publications

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“…The second method involves the calculations with fully relativistic small-core ECP (ECP28MDF) obtained by Lim et al [61,62], such that all 4s, 4p and 5s electrons (19) of Rb and Sr are correlated on both atoms.The PECs for the X 2 Σ + ground state and for the lowest quartet Σ + and Π states are determined within the open-shell spinrestricted coupled-cluster (RCC) theory [63] with single, double and triple excitations (RCCSD(T)) as in Ref. 19 implemented in the Molpro 2012 package [64].…”

Section: Methodsmentioning

confidence: 99%

“…In comparison to this work, we performed the calculations with significantly improved basis set in order to estimate the error attributed to the basis set incompleteness. We used the original uncontracted basis sets of Lim et al [61,62] to which we have added d, f and g Gaussian-type basis functions to improve core-valence correlation between the 4s and 4p shells with the 5s one. We also added a series of diffuse spdf g basis functions to better describe the dispersion interaction.…”

Section: Methodsmentioning

confidence: 99%

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Ground- and excited-state properties of the polar and paramagnetic RbSr molecule: A comparative study

2014

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This paper deals with the electronic structure of RbSr, a molecule possessing both a permanent magnetic and electric dipole moment in its own frame allowing its manipulation with external fields. Two complementary ab-initio approaches are used for the ground and lowest excited states: first, an approach relying on optimized effective core potentials with core polarization potentials based on a full configuration interaction involving three valence electrons, and second, an approach using a small-size effective core potential with 19 correlated electrons in the framework of coupled-cluster theory. We have found excellent agreement between these two approaches for the ground state properties including the permanent dipole moment. We have focused on studies of excited states correlated to the two lowest asymptotes Rb(5p 2 P )+Sr(5s 2 1 S) and Rb(5s 2 S)+Sr(5s5p 3 P ) relevant for ongoing experiments on quantum degenerate gases. We present also the Hund c) case potential curves obtained using atomic spin-orbit constants. These potential curves are an excellent starting point for experimental studies of molecular structure of RbSr using high-resolution spectroscopy.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Ground- and excited-state properties of the polar and paramagnetic RbSr molecule: A comparative study

2014

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“…For both barium and rubidium we used the spdf g quality basis sets suggested in Refs. [44,45]. The full basis of the dimer was used in the supermolecule calculations and the Boys and Bernardi scheme was used to correct for the basis-set superposition error [47].…”

Section: A Electronic Structure Calculationsmentioning

confidence: 99%

“…For Ba and Rb we took the ECP46MDF [44] and ECP28MDF [45] pseudopotentials, respectively, from the Stuttgart library. For both barium and rubidium we used the spdf g quality basis sets suggested in Refs.…”

Section: A Electronic Structure Calculationsmentioning

confidence: 99%

Sympathetic cooling of the Ba+ion by collisions with ultracold Rb atoms: Theoretical prospects

et al. 2011

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State-of-the-art ab initio techniques have been applied to compute the potential energy curves of the (BaRb) + molecular ion in the Born-Oppenheimer approximation for the singlet and triplet states dissociating into the ground state 1 S Rb + ion and the Ba atom in the ground 1 S state, the lowest singlet or triplet D excited states, and for the singlet and triplet states dissociating into the ground state 2 S Rb atom and the ground state 2 S Ba + ion. The ground state potential energy was obtained with the coupled cluster method restricted to single, double, and nonperturbative triple excitations. The first triplet states in the Σ, Π, and ∆ symmetries were computed with the restricted open-shell coupled cluster method restricted to single, double, and nonperturbative triple excitations. All other excited state potential energy curves were computed using the equation of motion approach within the coupled-cluster singles, doubles, and linear triples framework.The long-range coefficients describing the electrostatic, induction, and dispersion interactions at large interatomic distances are also reported. The electric transition dipole moments governing the X 1 Σ → 1 Σ, 1 Π have been obtained as the first residue of the polarization propagator computed with the linear response coupled-cluster method restricted to single and double excitations. Nonadiabatic radial and angular coupling matrix elements, as well as the spin-orbit coupling matrix elements have been evaluated using the multireference configuration interaction method restricted to single and double excitations with a large active space. With these couplings, the spin-orbit coupled (relativistic) potential energy curves for the 0 + and 1 states relevant for the running experiments have been obtained. Finally, relativistic transition moments and nonadiabatic coupling matrix elements were obtained from the nonrelativistic results and spin-orbit eigenvectors. The electronic structure input has been employed in the single channel scattering calculations of the collisional cross sections between the Ba + ion and Rb atom. Both nonrelativistic and relativistic potentials were used in these calculations. Our results show that the inelastic cross section corresponding to the charge transfer from the Rb atom to the Ba + ion is much smaller than the elastic one over a wide range of energies up to 1 mK. This suggests that sympathetic cooling of the Ba + ion by collisions with ultracold Rb atoms should be possible.2

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“…Energy-consistent PPs in their most recent variant are adjusted to reference data taken from multi-configuration (MC) Dirac-Hartree-Fock (DHF) calculations using the Dirac-Coulomb (DC) Hamiltonian and including perturbative estimates of the Breit interaction (+B). Finite nucleus effects are usually also included, as well as sometimes higher order relativistic corrections [25,26,27,28,29,30,31,32,33,34].…”

Section: Introductionmentioning

confidence: 99%

Efficient quantum chemical valence-only treatments of lanthanide and actinide systems

Dolg¹

2012

AIP Conference Proceedings

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Abstract. Recent progress in the development of lanthanide and actinide relativistic energy-consistent ab initio pseudopotentials is reported. Lanthanide 4f-in-core and actinide 5f-in-core pseudopotentials form an efficient tool for quantum chemical ab initio and first-principles calculations on larger systems, whenever the detailed electronic structure of the f shell is not of primary interest. The reliability of the 4f-in-core approximation is demonstrated for molecular lanthanide trihalides by comparison of calculated structural data with recommended experimental values. Due to the scarceness of experimental reference data the calibration of the 5f-in-core approximation is performed with respect to results from other more rigorous calculations. Lanthanide 4f-in-valence and actinide 5f-in-valence pseudopotentials allow the study of individual electronic states arising from a given f occupancy in a system. Recent progress to develop highly accurate small-core pseudopotentials which model all-electron calculations using the Dirac-Coulomb-Breit Hamiltonian is summarized and first applications are outlined.

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All-electron and relativistic pseudopotential studies for the group 1 element polarizabilities from K to element 119

Cited by 296 publications

References 47 publications

Ground- and excited-state properties of the polar and paramagnetic RbSr molecule: A comparative study

Ground- and excited-state properties of the polar and paramagnetic RbSr molecule: A comparative study

Sympathetic cooling of the Ba+ion by collisions with ultracold Rb atoms: Theoretical prospects

Efficient quantum chemical valence-only treatments of lanthanide and actinide systems

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