0000000000681182

AUTHOR

Pekka Pyykkö

A very short uranium-uranium bond: The predicted metastable U22+

Quantum chemical calculations, based on multiconfigurational wave functions and including relativistic effects, show that the U(2)2+ system has a large number of low-lying electronic states with S of 0 to 2 and Lambda ranging from zero to ten. These states share a very small bond length of about 2.30 A, compared to 2.43 A in neutral U2. The Coulomb explosion to 2 U+ lowers the energy by only 1.6 eV and is separated by a broad barrier.

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Theoretical search for very short metal-actinide bonds: NUIr and isoelectronic systems.

, respectively. These analogues provide anexample ofthe isolobal principle, now without any outsideligands onthePt atom,asituation describedasits “autogenicisolobality”. These systems have multiple C Pt bonds. Theisolobal principle of Hoffmann refers to the similar chemicalbehaviorofansphybridandametalatomwithligands,-ML

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1H and13C n.m.r. spectra of dichloro(trans-2-chlorovinyl)arsine

Proton and carbon magnetic resonance spectra of Lewisite or dichloro(trans-2-chlorovinyl)arsine have been measured and the results are compared with the n.m.r. spectral parameters of other trans-1,2-substituted ethylenes. The coupling constants can be rationalized by substituent electronegativity. The chemical shifts show an unusually large paramagnetic effect from the AsCl2 group.

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Large shape staggering in neutron-deficient Bi isotopes

The changes in the mean-square charge radius (relative to 209Bi), magnetic dipole, and electric quadrupole moments of 187,188,189,191Bi were measured using the in-source resonance-ionization spectroscopy technique at ISOLDE (CERN). A large staggering in radii was found in 187,188,189Big, manifested by a sharp radius increase for the ground state of 188Bi relative to the neighboring 187,189Big. A large isomer shift was also observed for 188Bim. Both effects happen at the same neutron number, N=105, where the shape staggering and a similar isomer shift were observed in the mercury isotopes. Experimental results are reproduced by mean-field calculations where the ground or isomeric states were…

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A small spherical liquid: A DFT molecular dynamics study of WAu12

The finite-temperature dynamics of WAu12, incorporating both electronic and structural effects, is studied using a density-functional-based Born-Oppenheimer molecular dynamics method. Molecular dynamics simulations for monomolecular WAu12 suggest a surface-melting-type behaviour of the angular degrees of freedom between 366 and 512 K. Thermally averaged electron density-of-states of WAu12 are compared to the experimental photoelectron spectra of WAu12(-).

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