Events Calendar

Alexander Rusakov, Assistant Professor at Oakland University
For more information on Dr. Rusakov's research, visit: https://sites.google.com/oakland.edu/rusakov/

Title: "Towards predictive heavy-element chemistry modeling: From basis sets to superheavy elements identification"

Strong relativistic effects in heavy elements challenge the traditional idea of the periodic law and put to the test the methodology of modern quantum chemistry. The unreliability of commonly perceived periodic trends manifests already around Z=85 and may break down in superheavy elements (Z≥104), where the effects of relativity become extreme. However, the chemical homology of superheavy elements remains crucial in designing experiments for their detection and interpreting the outcomes of such experiments. Establishing this homology with available quantum-chemical methods poses significant challenges.

In this presentation, I will outline the shortcomings of modern quantum-chemical approaches to predictive modeling of complex heavy-element chemistry. Using astatine, the heaviest halogen with promising medical applications, as an example, I will describe recent progress in developing high-quality basis sets for relativistic DFT (RDFT) with the particle swarm global optimization algorithm. Using properly assessed exchange-correlation functional approximations for RDFT, I will present the results from newly developed force fields to simulate the behavior of At^– in water. [1]

Using the refined RDFT approaches [1] backed up by relativistic coupled-cluster calculations, I will also present a comprehensive computational study of astatine’s behavior in thermochromatographic experiments on a gold surface and discuss the potential use of At as a non-intuitive chemical homolog of the superheavy element nihonium (Nh, Z=113) and the perspectives of its chemical identification. [2]

References

1. K.J.R. Espinosa, A.A. Kananenka, A.A. Rusakov, J. Chem. Theory Comput.

19, 7998–8012 (2023).

2. Yu.A. Demidov, A. Shalaevsky, A. Oleynichenko, A.A. Rusakov, Phys. Chem. Chem. Phys. 26, 23823–23834 (2024).