Relativistic all-electron <i>ab initio</i> calculations of CsHg potential energy curves including spin-orbit effects

Polly, Robert; Gruber, Dieter; Windholz, Laurentius; Gleichmann, M.; Heß, Bernd A.

doi:10.1063/1.476514

Cited by 9 publications

(5 citation statements)

References 47 publications

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“…Other workers have also experimented with mean field or one center approximations to the two electron term. [25][26][27] An alternative operator consisting of only a one electron term can be obtained from the difference of effective core potentials for different spinors, obtained from atomic calculations with the Dirac-Coulomb equation 28 or the Wood-Boring Hamiltonian. 29 Recently a gradient program has been developed for this kind of operator 30 to permit geometry optimization with spin-orbit effects.…”

Section: Introductionmentioning

confidence: 99%

Spin−Orbit Splittings in the Third-Row Transition Elements: Comparison of Effective Nuclear Charge and Full Breit−Pauli Calculations

et al. 2001

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The spin−orbit splittings of low-lying states in third-row transition elements were calculated using both an effective core potential (ECP) method within the one-electron (Zeff) approximation and all-electron (AE) methods using three different approaches. The wave functions were obtained using the multiconfiguration self consistent field (MCSCF) method followed by second-order configuration interaction (SOCI) calculations. All calculated results, except for the ones on atomic Ir, are in reasonable agreement with the corresponding experimental observations. The unsatisfactory results for atomic Ir are attributed to the poor theoretical prediction of the adiabatic energy gap between the lowest two 4F states. This gap has an incorrect sign in AE calculations without scalar relativistic corrections, but the gap can be reproduced qualitatively if these corrections are added using the newly developed RESC (relativistic elimination of small components) scheme. As a result, the AE calculations with the RESC approximation give spin−orbit splittings similar to those obtained by the ECP calculations with the Zeff approximation. Disciplines Chemistry CommentsReprinted (adapted) The spin-orbit splittings of low-lying states in third-row transition elements were calculated using both an effective core potential (ECP) method within the one-electron (Z eff ) approximation and all-electron (AE) methods using three different approaches. The wave functions were obtained using the multiconfiguration self consistent field (MCSCF) method followed by second-order configuration interaction (SOCI) calculations. All calculated results, except for the ones on atomic Ir, are in reasonable agreement with the corresponding experimental observations. The unsatisfactory results for atomic Ir are attributed to the poor theoretical prediction of the adiabatic energy gap between the lowest two 4 F states. This gap has an incorrect sign in AE calculations without scalar relativistic corrections, but the gap can be reproduced qualitatively if these corrections are added using the newly developed RESC (relativistic elimination of small components) scheme. As a result, the AE calculations with the RESC approximation give spin-orbit splittings similar to those obtained by the ECP calculations with the Z eff approximation.

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Section: Introductionmentioning

confidence: 99%

Spin−Orbit Splittings in the Third-Row Transition Elements: Comparison of Effective Nuclear Charge and Full Breit−Pauli Calculations

et al. 2001

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“…In addition to the atomic and molecular systems that contain heavy elements, the DK2 method was applied to crystalline systems with the crystal orbital approach under periodic boundary conditions . Their applications include the calculation of spectroscopic constants − such as molecular geometries, frequencies, and dissociation energies, fine structure splittings, , electronic excitation energies, − laser-induced chemiluminescence, , ionization potentials, and electron affinities, as well as electrical properties such as dipole moments, dynamic multipole polarizabilities, dispersion coefficients, − and nuclear quadrupole coupling tensors. , Independent of the work in the Hess group, the DK2 approach was implemented in the framework of the linear combination of Gaussian-type orbitals (LCGTO) approach to density functional theory (DFT) by the Rösch group . Rösch and co-workers applied their LCGTO–DFT approach using the DK2 method to the electronic structure investigations of large molecular systems − and diatomic molecules. − …”

Section: Theoretical Aspectsmentioning

confidence: 99%

The Douglas–Kroll–Hess Approach

2011

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of the Small Component 390 2.3.6. Infinite-Order Two-Component Method 391 2.4. ElectronÀElectron Interaction in the DK Hamiltonian 391 2.5. SpinÀOrbit Effects 392 3. Practical Aspects 393 3.1. Implementation of the DK Hamiltonian 393 3.2. Energy Derivatives 394 3.3. Basis Sets 395 3.4. Model Potentials 395 3.5. Program Packages 396 4. Magnetic Properties with the DK Method 396 4.1. NMR Magnetic Shielding Constants 396 4.2. NMR SpinÀSpin Couplings 397 4.3. Magnetizabilities 397 4.4. Zero-Field Splittings 398 4.5. EPR g-Tensors 398 4.6. Hyperfine Coupling Tensors 398 4.7. Magnetic Circular Dichroisms 399 5. Conclusions and Perspectives 399 Biographies 399 Acknowledgment 400 References 400

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“…for Hg). Interestingly, Polly et al [42] have obtained a very shallow ground-state potential for the CsHg molecule (160 cm −1 ) but such disagreement might be explained by the fact that no triply excited configurations were included by these authors.…”

Section: Ab-initio Interaction Potentialsmentioning

confidence: 99%

“…The best studied system to date is Li+Hg, for which the results of bound-bound and bound-free fluorescence spectroscopy were corroborated by high-quality quantum chemical calculations of the lowest excited states [40,41]. High-quality relativistic studies of the CsHg system were performed by Polly et al [42].…”

Section: Introductionmentioning

confidence: 99%

Optical Feshbach resonances and ground-state-molecule production in the RbHg system

et al. 2017

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We present the prospects for photoassociation, optical control of interspecies scattering lengths and finally, the production of ultracold absolute ground state molecules in the Rb+Hg system. We use the "gold standard" ab initio methods for the calculations of ground (CCSD(T)) and excited state (EOM-CCSD) potential curves. The RbHg system, thanks to the wide range of stable Hg bosonic isotopes, offers possibilities for mass-tuning of ground state interactions. The optical lengths describing the strengths of optical Feshbach resonances near the Rb transitions are favorable even at large laser detunings. Ground state RbHg molecules can be produced with efficiencies ranging from about 20% for deeply bound to at least 50% for weakly bound states close to the dissociation limit. Finally, electronic transitions with favorable Franck-Condon factors can be found for the purposes of a STIRAP transfer of the weakly bound RbHg molecules to the absolute ground state using commercially available lasers.

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Relativistic all-electron ab initio calculations of CsHg potential energy curves including spin-orbit effects

Cited by 9 publications

References 47 publications

Spin−Orbit Splittings in the Third-Row Transition Elements: Comparison of Effective Nuclear Charge and Full Breit−Pauli Calculations

Spin−Orbit Splittings in the Third-Row Transition Elements: Comparison of Effective Nuclear Charge and Full Breit−Pauli Calculations

The Douglas–Kroll–Hess Approach

Optical Feshbach resonances and ground-state-molecule production in the RbHg system

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