FIRST PRINCIPLE BASED MODELING AND INTERPRETATION OF CHEMICAL EXPERIMENTS ON SUPERHEAVY ELEMENT IDENTIFICATION
A.V. Zaitsevskii, Yu.A. Demidov, N.S. Mosyagin, L.V. Skripnikov, A.V. Titov
Received: 17 MAR 2015,
Received revised: 29 APR 2015,
Accepted: 8 MAY 2015,
Published online: 18 OCT 2016
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Our latest advances in studies of actinide and superheavy element (SHE) chemistry using the shape-consistent two-component small-core relativistic pseudopotential (RPP) method and two-component relativistic density functional theory (2c–RDFT) are summarized. The features of these elements, due to large relativistic effects, are emphasized. The RPP model, leaving for explicit correlation treatment with both valence and subvalence (outercore) electrons, accounts for the finite nuclear size and incorporates relativistic effects (including the bulk of Breit interactions), providing a good basis for attaining optimal accuracy/cost ratio in the cases of large and strongly interfering relativistic and correlation effects, intrinsic for the heavy-atom compounds. The RPP/2c–RDFT approach allows one to solve the outercore-valence many-electron problem with moderate computational expenses while using practically exhaustive basis sets, optimized for the case of large differences between nl(j=l+1/2) and nl(j=l-1/2) one-electron states. Because of the exceptional role of thermochromatography on gold in the experiments on the “chemical” identification of SHEs with atomic numbers Z ≥ 112, the main attention was paid to the description of the SHE – gold interactions. Adsorption energies of SHEs on a gold surface were estimated using the cluster model. Its reliability was improved by monitoring the charge distributions in the vicinity of the adsorption site, taking account of the effects of the relaxation of the cluster compatible with its embedding into the crystal. The resulting desorption energy estimates for elements 113 and 120 single atoms from gold surface are substantially lower than the previously reported values.
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