Taming the Electronic Structure of Lead and Eka-lead (Flerovium) by the Relativistic Coupled Cluster Method

Abstract

Theoretical investigations of the superheavy elements (SHEs) are extremely challenging and are often the sole source of useful chemical information. Relativistic Fock-space multireference coupled cluster (RFS-MRCC) computations have been carried out for evaluating the ionization potential (IP), excitation energies (EE), nuclear magnetic hyperfine constant (A), lifetime (τ), and Landé g factor of singly ionized eka-lead (Fl II). To judge the accuracy of Fl II results, similar calculations are performed for Pb II, which shows a nice and consistent agreement with known experimental values. Thus, we believe that our predictions for Fl are reliable and useful for the simulation of experimental behavior. To the best of our knowledge, no prior theoretical and/or experimental information is available for A, τ, and g-factor of this SHE. The higher IPs and EEs of Fl II, with respect to Pb II, indicate the former to be more inert and less metallic than Pb. This is contingent on the effects of the relativistic stabilization of the 7s and 7p1/2 orbitals. The present analysis demonstrates the influence of higher-body cluster operators on atomic properties. The close agreement with the experiment (having an estimated error within 1-2%) indicates that the FS-MRCC method is a reliable predictive tool in cases where the experimental results are not readily available, such as the SHEs. The remaining source of error possibly stems out from the omission of the full-blown triple virtual excitations and the absence of Breit interaction.

Theoretical Search for the Highest Valence States of the Coinage Metals: Roentgenium Heptafluoride May Exist

“…Against this backdrop, one might reasonably expect that seventh-period elements will furnish their own share of molecules with unexpected valence states. A striking finding in this connection is that the group 14 element flerovium is volatile, consistent with a noble-gas-like zero-valent state, a result of the very large 7p 1/2–3/2 splitting. − Another striking, albeit as yet experimentally unverified, prediction is that copernicium tetrafluoride (CnF 4 ) should be much more stable than HgF 4 with respect to F 2 elimination . Herein, we report a relativistic DFT study of the penta- and heptavalent states of gold and roentgenium using the ZORA , ­(zeroth order regular approximation to the Dirac equation) Hamiltonian, including spin–orbit coupling at the two-component level, and large all-electron relativistic Slater-type quadruple-ζ quadruple polarization (ZORA-STO-QZ4P) basis sets.…”

Reappraisal of Nuclear Quadrupole Moments of Atomic Halogens via Relativistic Coupled Cluster Linear Response Theory for the Ionization Process

“…The FS-MRCC based expectation value approach has also been used to compute the one-electron properties of atomic systems . Recently, the FS-MRCC method with four-component relativistic spinors has emerged as a method of choice for interpretation of the spectral properties of various relativistic systems. ,,− Though the properties resulting from this approach are found to be quite reasonable, the method suffers from intrinsic uncertainties as the numerator and the denominator appearing in the expression of property are nonterminating by construction.…”