Molecular structure of XeF6

Pitzer, Kenneth S.; Bernstein, Lawrence S.

doi:10.1063/1.431880

Cited by 124 publications

(132 citation statements)

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“…For instance, studies on Cn suggest mercury-like properties, [18,19] whereas other studies suggest noble-gas-like behavior, mainly due to the strong relativistic contraction of the 7s orbital. [20,21] Exploring the properties of complexes of the superheavy elements using relativistic theoretical calculations is therefore important to understand their chemistry and our understanding of the chemistry of the superheavy elements in general. In this study, we report the structural parameters, vibrational frequencies, bond dissociation energies and electronic absorption spectra of monocyanide and dicyanide complexes of darmstadtium, roentgenium, and copernicium.…”

Section: Introductionmentioning

confidence: 99%

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Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

Demissie

Ruud

2017

Int J of Quantum Chemistry

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We report the structures and properties of the cyanide complexes of three superheavy elements (darmstadtium, roentgenium, and copernicium) studied using two-and four-component relativistic methodologies. The electronic and structural properties of these complexes are compared to the corresponding complexes of platinum, gold, and mercury. The results indicate that these superheavy elements form strong bonds with cyanide. Moreover, the calculated absorption spectra of these superheavy-element cyanides show similar trends to those of the corresponding heavyatom cyanides. The calculated vibrational frequencies of the heavy-metal cyanides are in good agreement with available experimental results lending support to the quality of our calculated vibrational frequencies for the superheavy-atom cyanides.copernicium, darmstadtium, relativistic DFT, roentgenium, superheavy elements | I N TR ODU C TI ONThe term heavy atom refers roughly to elements in the fourth to sixth periods of the periodic table, whereas elements in the seventh period are called superheavy elements. Heavy-element compounds have been rather extensively studied [1][2][3][4][5][6][7] compared to the superheavy ones. This is due to the abundance of the heavy elements and the many uses of heavy-element compounds; for instance, gold dicyanide (AuðCNÞ 2 2 ) was used in gold mining, [8,9] platinum cyanides are used in nanomaterials, [10] whereas mercury(II) cyanide (HgðCNÞ 2 ) was used as an antiseptic [11] until this was stopped due to its toxicity. [12] In contrast, the lack of a natural abundance of the superheavy elements has limited the number of studies of compounds involving these superheavy elements. In particular, with the exception of RgCN, [6] there has been no studies of the cyanide complexes of Ds, Rg, and Cn reported previously in the literature. Patzschke and Pyykk€ o [13] studied the properties of darmstadtium carbonyl and carbide and compared them to platinum carbide and carbonyl and found that darmstadtium resembled platinum in its bonding properties. [13] Theoretical studies of darmstadtium hexafluoride (DsF 6 ) and darmstadtium tetrachloride (DsCl 4 ) have also been reported and these compounds have been shown to have properties similar to those of the lighter group analogues. [14][15][16] The structure and bonding properties of roentgenium monocyanide have been compared with the cyanides of copper, silver, and gold. [6] Theoretical studies on the electronic structures of RgX (X 5 H, F, Cl, Br, O, Au, or Rg) have also been reported [5] where the RgAH bond in RgH was found to be strong due to relativistic effects, 153.0 pm using ZORA and 150.3 pm using spin-orbit pseudopotential coupled cluster calculations, in contrast to 190.8 pm using nonrelativistic calculations (a 27% relativistic bond-length contraction). Calculations using two-component spin-orbit-coupled relativistic energy-adjusted pseudopotentials showed that the CnAH bond length in CnH 1 is shorter than the ZnAH bond length in ZnH 1 . [17] The calculated equilibrium bond d...

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

Demissie

Ruud

2017

Int J of Quantum Chemistry

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“…To our knowledge, starting from the papers of Pitzer 6 and Fricke 7 in 1975 it was mainly suggested by other authors that E112 behaves rather like a rare gas than Hg. In Ref.…”

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Is E112 a relatively inert element? Benchmark relativistic correlation study of spectroscopic constants in E112H and its cation

Mosyagin

Isaev

Титов

2006

The Journal of Chemical Physics

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“…11,12 Due to strong relativistic effects, it is also known that the behavior of the SHE does not necessarily follows the known trends for lighter homologues in chemical groups, and forecasting of properties and trends based on simple extrapolations of properties of lighter homologues may result in erroneous predictions. 13 In fact, the chemistry of SHE may be a lot of different to what is known due to these strong relativistic effects 14 and perform relativistic calculations is often the only source of useful chemical information. 7 From all possible options used for the inclusion of relativistic effects, the most reliable is the 4-component relativistic method, 12,15 where the relativistic effects of interest for chemistry as spin-orbit or mass-velocity are included from the onset.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio correlated all electron Dirac-Fock calculations for eka-francium fluoride (E119F)

Miranda

Mendes

Gomes

et al. 2012

J. Braz. Chem. Soc.

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Resultados obtidos por cálculos Dirac-Fock correlacionados de 4 componentes para o fluoreto do elemento E119 (Eka-Frâncio) com base estável e precisa, livre de prolapso variacional, são reportados neste trabalho. No nível CCSD(T), a distância de equilíbrio R e , frequência harmônica w e e energia de dissociação D e são 2,432 Å, 354,97 cm -1 e 116,92 kcal mol -1 , respectivamente. Também são reportados base livre de prolapso variacional de 4 componentes para o elemento 119, uma curva analítica de energia potencial precisa e o espectro vibracional a partir dos dados obtidos no nível CCSD(T). Nossos resultados sugerem que a molécula E119F deva ser menos iônica que seus fluoretos alcalinos homólogos mais leves, em contraste com o senso químico comum baseado nas propriedades periódicas -era de se esperar nesta molécula a ligação química mais iônica possível. Também encontramos que a correção do tipo modelo de carga para negligenciar as integrais do tipo SS resulta em erros insignificantes e acelera os cálculos cerca de 3 vezes no nível CCSD(T) e cerca de 4 vezes no nível DFT/B3LYP.Results obtained with correlated 4-component Dirac-Fock calculations for element E119 (ekafrancium) fluoride with stable and accurate basis set (prolapse-free) are reported in this work. At CCSD(T) level, the equilibrium distance R e , harmonic frequency w e and dissociation energy D e are 2.432 Å, 354.97 cm -1 and 116.92 kcal mol -1 , respectively. A 4-component prolapse free basis set for E119, an accurate analytical potential energy curve and vibrational spectra from CCSD(T) data are also reported. Our results suggest that E119F should be less ionic than lighter alkaline fluoride homologues, in contrast to the common chemical belief based on periodic trends -it would be expected in this molecule the most ionic bond possible. We also found that the charge model correction to neglect SS integrals leads to negligible errors and speed up calculations close to three times at CCSD(T) level and close to 4 times at DFT/B3LYP level. Keywords: super heavy elements (SHE), 4-component relativistic molecular calculations, 4-component gaussian basis sets, relativistic effects in chemistry IntroductionThe quest for super heavy nuclei began in 1940's with the synthesis of new elements with an atomic number greater than uranium, and the search for new elements was boosted with the prediction of an "island of stability" 1 for super heavy elements (SHE) with atomic numbers 114,120 and 126. [2][3][4] Some predictions estimate half-lives for isotopes with special combination of proton and neutron numbers as long as 10 8 years, as for 290 Sg 184 . 5,6 Recently, the production of the super heavy elements 112 through 118 using "hot" fusion reactions attained special chemical interest since the reported half-lives are in order of seconds, orders of magnitude longer than those of isotopes produced by "cold" fusion reactions. In addition to short half-lives, the drawback of low production rates also makes chemical experiments expensive, difficult and hard to perfo...

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Molecular structure of XeF6

Cited by 124 publications

References 23 publications

Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

Is E112 a relatively inert element? Benchmark relativistic correlation study of spectroscopic constants in E112H and its cation

Ab Initio correlated all electron Dirac-Fock calculations for eka-francium fluoride (E119F)

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