Spin−Orbit Effects, VSEPR Theory, and the Electronic Structures of Heavy and Superheavy Group IVA Hydrides and Group VIIIA Tetrafluorides. A Partial Role Reversal for Elements 114 and 118

Nash, Clinton S.; Bursten, Bruce E.

doi:10.1021/jp982735k

Cited by 50 publications

(35 citation statements)

References 33 publications

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“…In the light of the atomic results above, this is not surprising: the bond length is too short for the 8s to have a significant bonding effect, and the cost of promotion is too high. This is at variance with the findings of Nash and Bursten for 117H [12], whose work is based on spin-orbit CI based on spinfree calculations with an AREP. It is possible that the analysis in terms of spin-free eigenfunctions or the AREP itself places too much emphasis on the 8s.…”

Section: Hydridescontrasting

confidence: 82%

“…This indicates that bonding involves both the valence and subvalence spinors, much more so than for 114H. The result for 114H is somewhat at variance with previous work, for which a minimum around 195-200 pm with a dissociation energy from 0.2-0.5 eV is found [6,12,16,18], based on DFT or CCSD(T) calculations. The CCSD(T) calculations are on the lower end of this range, whereas DFT gives larger values and is likely to overestimate the binding.…”

Section: Hydridessupporting

confidence: 57%

“…The principal characteristics of the chemistry of the 7p block have been discussed in detail by others [6,10,12,14,19] and will only be summarized here. These characteristics will be used to guide the discussion of the results.…”

Section: Applicationsmentioning

confidence: 99%

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Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the 7p elements, with atomic and molecular applications

Dyall

2012

Theor Chem Acc

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Relativistic basis sets of double-zeta, triplezeta, and quadruple-zeta quality have been optimized for the 7p elements at the Dirac-Coulomb self-consistent field level of theory with a Gaussian nuclear charge distribution. For all of these sets, valence and outer-core correlating functions have been optimized in multireference CI calculations on the valence p n states. Diffuse functions are also provided. Prescriptions are given for constructing contracted basis sets, based on MRCI calculations for correlation of the atoms. The basis sets are applied to a range of atomic and molecular properties, to provide information on how to use the basis sets. Tests of the basis sets with an explicit representation of the 8s showed that the 8s is not needed. The basis sets are available as an internet archive and from the Dirac program web site, http://dirac.chem.sdu.dk.

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Section: Hydridescontrasting

confidence: 82%

Section: Hydridessupporting

confidence: 57%

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Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the 7p elements, with atomic and molecular applications

Dyall

2012

Theor Chem Acc

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“…Influence of the SO interaction on the geometry of 118F 4 was investigated by RECP-SOCI and -CCSD calculations [147,159,160]. It was shown that a D 4h geometrical configuration known for XeF 4 and RnF 4 becomes about 0.2 eV less stable than the T d one.…”

Section: P Elementsmentioning

confidence: 99%

Relativistic electronic structure studies on the heaviest elements

Pershina¹

2011

Radiochimica Acta

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Summary. Spectacular developments in relativistic quantum theory and computational algorithms in the last two decades allowed for accurate predictions of properties of the heaviest elements and their experimental behaviour. The most recent works in this area of investigations are overviewed. Preference is given to those related to experimental research. The role of relativistic effects is elucidated.

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“…Experimental excited levels in free Pb atoms could be reproduced in calculations to 0.06 eV [16]. Comparison of some ionization potential values [16][17][18], is shown in Table 2. The potentials for SHE seem trustworthy because of good agreement with experimental data for the known homologues.…”

Section: Chemistry Of She -Theorymentioning

confidence: 98%

State of art in experimental studies and theory of superheavy elements

Zvára

2003

Czech J Phys

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A few recent years have seen remarkable progress in synthesising new, "superheavy" elements (SHE). Researchers at Dubna reached the slopes of the expected "island of stability" around Z = 114 and N = 184. In weeks to months bombardments of isotopes of U, Pu and Cm by very intense beams of 48Ca, they discovered (mostly s-active) isotopes of previously unknown elements 116 and 114, as well as of element 112, all with relatively very long half-lives -up to minutes. Modem theory approaches two orders of magnitude accuracy in predicting spontaneous fission and s-decay half-lives of even-even superheavy nuclides.The findings of physical experiments give an impetus to chemical studies. Quantum (theoretical) chemistry studies aim at the problem of "relativistic effects" in chemical properties of SHE to provide also some hints for experiments. As yet, only structure and energy levels of SHE atoms, and simple molecules containing light ligands can be calculated with a necessary accuracy while experimenters have to do with more complex free molecules or ions in solutions, and heavier ligands. Work on chemical identification of the 3-min 283112 is in progress at Dubna. Being a homologue of Hg, element 112 must be even more volatile metal. Thank to this, its single atoms can be easily separated from interfering activities. The first results with a few atoms of element 112 indicate that at certain experimental conditions this element behaves more like radon rather than mercury.

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Spin−Orbit Effects, VSEPR Theory, and the Electronic Structures of Heavy and Superheavy Group IVA Hydrides and Group VIIIA Tetrafluorides. A Partial Role Reversal for Elements 114 and 118

Cited by 50 publications

References 33 publications

Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the 7p elements, with atomic and molecular applications

Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the 7p elements, with atomic and molecular applications

Relativistic electronic structure studies on the heaviest elements

State of art in experimental studies and theory of superheavy elements

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