Theoretical molecular spectroscopy of actinide compounds: the ThO molecule

Zaitsevskii, Andréi; Oleynichenko, Alexander V.; Eliav, Ephraim

doi:10.1080/00268976.2023.2236246

Molecular Physics

2023

DOI: 10.1080/00268976.2023.2236246

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Theoretical molecular spectroscopy of actinide compounds: the ThO molecule

Andréi Zaitsevskii

Alexander V. Oleynichenko

Ephraim Eliav

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Cited by 7 publications

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Ab initiostudy of electronic states and radiative properties of the AcF molecule

Skripnikov,

Oleynichenko,

Zaitsevskii

et al. 2023

The Journal of Chemical Physics

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Relativistic coupled-cluster calculations of the ionization potential, dissociation energy, and excited electronic states under 35 000 cm−1 are presented for the actinium monofluoride (AcF) molecule. The ionization potential is calculated to be IPe = 48 866 cm−1, and the ground state is confirmed to be a closed-shell singlet and thus strongly sensitive to the T,P-violating nuclear Schiff moment of the Ac nucleus. Radiative properties and transition dipole moments from the ground state are identified for several excited states, achieving a mean uncertainty estimate of ∼450 cm−1 for the excitation energies. For higher-lying states that are not directly accessible from the ground state, possible two-step excitation pathways are proposed. The calculated branching ratios and Franck–Condon factors are used to investigate the suitability of AcF for direct laser cooling. The lifetime of the metastable (1)3Δ1 state, which can be used in experimental searches of the electric dipole moment of the electron, is estimated to be of order 1 ms.

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Ab initiostudy of electronic states and radiative properties of the AcF molecule

Skripnikov,

Oleynichenko,

Zaitsevskii

et al. 2023

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

Error of relativistic effective core potentials for closed-shell diatomic molecules of p-block heavy and superheavy elements in DFT and TDDFT calculations

Lu,

Wang,

Wang

2023

The Journal of Chemical Physics

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Pseudopotentials (PP) are extensively used in electronic structure calculations, particularly for molecules containing heavy elements. Parameters in PPs are mainly determined from ab initio results, and errors of such PPs in density functional theory (DFT) calculations have been studied previously. However, PP errors on results with spin–orbit coupling and those in time-dependent DFT (TDDFT) calculations have not been reported previously. In this work, we investigate the error of the small-core energy-consistent Stuttgart/Koln pseudopotentials in DFT and TDDFT calculations with and without spin–orbit coupling. Ground state bond lengths, harmonic frequencies, dissociation energies, and vertical excitation energies for a series of closed-shell diatomic heavy and superheavy p-block molecules are calculated using several popular exchange-correlation functionals. PP errors are estimated by comparing with results using the all-electron Dirac–Coulomb (-Gaunt) Hamiltonian. Our results show that the difference between ground state properties and most excitation energies in scalar-relativistic calculations with the PP and those of all-electron calculations is quite small. This difference becomes somewhat larger when spin–orbit coupling (SOC) is present, especially for properties that are affected by SOC to some extent. In addition, the errors of the PPs are insensitive to the employed exchange-correlation functionals in most cases. Our results indicate that reasonable DFT and TDDFT results can be obtained using the small-core energy-consistent Stuttgart/Koln pseudopotentials for heavy and super-heavy p-block molecules.

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