On the Importance of 5d Orbitals for Covalent Bonding in Ytterbium Clusters

Wang, Yixuan; Schautz, Friedemann; Flad, Heinz-Jürgen; Dolg, Michael

doi:10.1021/jp9905169

Cited by 12 publications

(19 citation statements)

References 30 publications

(56 reference statements)

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“…Further applications we see, e.g. in the study of metal clusters of heavier actinides, similar to previous related work on ytterbium clusters [36]. In summary, we think that the range of possible successful applications of the actinide 5f-in-core PPs is certainly somewhat smaller than for lanthanide 4f-in-core PPs [37], which yield reliable results for almost 20 years [38].…”

Section: Range Of Applicationssupporting

confidence: 84%

Quasirelativistic 5f-in-core pseudopotential study of the actinocenes An(C8H8)2, An=Th–Pu

Moritz

Dolg

2007

Chemical Physics

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Section: Range Of Applicationssupporting

confidence: 84%

Quasirelativistic 5f-in-core pseudopotential study of the actinocenes An(C8H8)2, An=Th–Pu

Moritz

Dolg

2007

Chemical Physics

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“…It has been shown that covalent bonding can be described in terms of charge fluctuations [32], which in the case of Lu 2 , depends strongly on the participation of 5d orbitals in bonding. Wang et al have already reported a significant contribution of 5d orbital to the covalent bonding in the case of ytterbium clusters [33]. A similar 5d contribution to Lu−Lu covalent bonding is thus expected.…”

Section: E Effects Of Hf Exchange On Covalent Bondingsupporting

confidence: 53%

Density Functional Study on Relative Energies, Structures, and Bonding of Low-lying Electronic States of Lutetium Dimer

Xia

Xiao

Zhang

et al. 2009

Chinese Journal of Chemical Physics

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Low-lying electronic states of the lutetium dimer (Lu 2 ) were studied based on density functional theory (DFT) using ten different density functionals together with three different relativistic effective core pseudopotentials (RECPs). Relative state energies, equilibrium bond lengths, vibrational frequencies, and ground-state dissociation energies were evaluated. It was found that the ground state is a triplet state irrespective of the type of functional and RECP used. This result is in contrast with a previous DFT calculation which gave a singlet ground state for Lu 2 . By comparing with the high-level ab initio and available experimental results, it is evident that the hybrid-GGA functionals combined with the Stuttgart smallcore RECP yield the best overall agreement for the properties under study. The effects of Hartree-Fock exchange in B3LYP functional on the calculated bond length and dissociation energy of the ground state were examined, and rationalized in terms of 5d participation in Lu−Lu covalent bonding.

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“…When the two Yb atoms approach each other, they create a weakly bonded, van der Waals‐type complex . It is well known that such weakly bonded compounds tend to be extremely sensitive to the quality of the atomic basis set and the (approximate) dynamic energy correction .…”

Section: Resultsmentioning

confidence: 99%

“…When the two Yb atoms approach each other, they create a weakly bonded, van der Waals-type complex. [33,36,81,82] It is well known that such weakly bonded compounds tend to be extremely sensitive to the quality of the atomic basis set and the (approximate) dynamic energy correction. [83] Thus, we first scrutinize the ground state potential energy surface obtained from the CCSD(T) approach before benchmarking various electron correlation methods for both ground and excited states.…”

Section: Toward a Reliable And Accurate Ground State Potential Enermentioning

confidence: 99%

Modeling the electronic structures of the ground and excited states of the ytterbium atom and the ytterbium dimer: A modern quantum chemistry perspective

Tecmer

Boguslawski

Borkowski

et al. 2019

Int J of Quantum Chemistry

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We present a comprehensive theoretical study of the electronic structures of the Yb atom and the Yb 2 molecule, respectively, focusing on their ground and lowest-lying electronically excited states. Our study includes various state-of-the-art quantum chemistry methods such as CCSD, CCSD(T), CASPT2 (including spin-orbit coupling), and EOM-CCSD as well as some recently developed pCCD-based approaches and their extensions to target excited states. Specifically, we scan the lowest-lying potential energy surfaces of the Yb 2 dimer and provide a reliable benchmark set of spectroscopic parameters including optimal bond lengths, vibrational frequencies, potential energy depths, and adiabatic excitation energies. Our in-depth analysis unravels the complex nature of the electronic spectrum of Yb 2 , which is difficult to model accurately by any conventional quantum chemistry method. Finally, we scrutinize the biexcited character of the first 1 Σ + g excited state and its evolution along the potential energy surface. K E Y W O R D S relativistic effects, electron corellation effects, spin-orbit coupling, equation of motion coupled cluster, CASPT2 | INTRODUCTIONThe divalent ytterbium atom has in recent years garnered significant attention thanks to its many uses in cold atom physics. It has a nonmagnetic 1 S 0 ground state and several useful optical transitions: the strong 1 S 0 $ 1 P 1 line can be used for Zeeman slowing, whereas the narrow (181 kHz) intercombination 1 S 0 $ 3 P 1 line can be used to directly laser cool Yb atoms to microkelvin temperatures. [1] Yb has seven stable isotopes: two fermions (171 and 173 with nuclear spins of 1/2 and 5/2, respectively) and five bosons (168, 170, 172, 174, and 176) that lack nuclear spin. The rich isotope structure makes it possible to mass-tune the atomic interactions [2] and facilitates a wide array of possible quantum-degenerate gases. [3][4][5][6] The doubly forbidden 1 S 0 $ 3 P 0 transition lies at the heart of optical atomic clocks [7] that are among the most precise physical instruments known to mankind. For example, an ytterbium clock has recently been demonstrated to enable geopotential measurements with an accuracy below a centimeter. [8] The long-lived 3 P 0 clock states also find use in quantum simulations using Yb atoms. [9] The long-range interactions in the Yb dimer have been probed extensively by high-resolution photoassociation spectroscopy (PAS) [10] near the narrow 1 S 0 $ 3 P 1 intercombination line. The excited 1 S 0 + 3 P 1 (0 + u ) [11,12] state has been probed by single color PAS and provided the van der Waals C 6 coefficient and an improved value of the atomic 3 P 1 lifetime. Two-color PAS of ground state 0 + g vibrational levels [2,13] delivered accurate

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On the Importance of 5d Orbitals for Covalent Bonding in Ytterbium Clusters

Cited by 12 publications

References 30 publications

Quasirelativistic 5f-in-core pseudopotential study of the actinocenes An(C8H8)2, An=Th–Pu

Quasirelativistic 5f-in-core pseudopotential study of the actinocenes An(C8H8)2, An=Th–Pu

Density Functional Study on Relative Energies, Structures, and Bonding of Low-lying Electronic States of Lutetium Dimer

Modeling the electronic structures of the ground and excited states of the ytterbium atom and the ytterbium dimer: A modern quantum chemistry perspective

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