Chemical Bonding Analysis for Complex Solids in Real Space
Solid State and Surface Chemistry, Material Synthesis
Theoretical Condensed Matter Physics
Final Report Abstract
Modern solid state chemistry is inconceivable without theoretical treatment of solids using efficient computational methods. Being deeply rooted in the formalism of reciprocal space physics, they often lack connections to familiar chemical concepts, indispensable for the chemical understanding of matter. The main aim of the project was to develop tools capable to recover a chemical view on the interactions of atoms within solids using the results of modern solid state computational methods. One of the main topic within our project was the extension of the powerful indicators developed earlier (delocalization indices, domain-averaged Fermi orbitals and other indicators within quantum theory of atoms in molecules - QTAIM) to the projector augmented wave (PAW) method. We have developed efficient computation algorithm for the core ingredient of these indicators – the domain overlap matrices and implemented them as a general purpose computational module able to process ABINIT code computational results. We have shown, that with that we can essentially speed up computations, reduce in the same time their memory footprint and thus open the way to the analysis of complex structures. In cooperation with the colleagues from TU Dresden and MPI for Chemical Physics of Solids we have applied these methods to the novel complex superconductors, topological insulators, fast ionic conductors which has enabled us in most of the cases to explain the properties of these compounds. Many intriguing solids being nowadays a hotspot of research contain heavy elements and thus experience essential relativistic effects which are responsible for their unique properties. As a second research direction of our project we have extended the formalism and developed indicators applicable on a firm theoretical ground to the state of the art computational techniques taking relativistic effects into account. We have applied these tools to the analysis heavy-element solids, mentioned in the previous paragraph and have found that even weak spin-relativistic effects are capable in certain cases enhance unusual properties of solids. It would be desirable to continue this line of research further since within this project we have been able to collect only rather limited experience on this topic. Relativistic effects is not the only complication known to be important for solids. Strong electron correlation is very often crucial to obtain even the qualitatively correct description for them. As a third research direction, we have developed and applied computational tools capable to characterize in the same time delocalization and chemical bonding in strongly correlated solids, i.e. Mott insulators. The analysis of 1D-3D hydrogen lattices as paradigmatic Mott insulators from numerical 1RDMFT computations has recovered chemically transparent description of the metal-insulator transition, consistent with Hubbard model analytic calculations. It would be desirable to extend this direction towards applications on realistic strongly correlated solids and related phenomena.
Publications
- Electron localizability indicators for spinor wavefunctions, J. Comput. Chem. 2014, 35, 565 – 585
A. I. Baranov
(See online at https://doi.org/10.1002/jcc.23524) - Domain overlap matrices from planewave-based methods of electronic structure calculation, J. Chem. Phys. 2016, 145, 154107
P. Golub, A. I. Baranov
(See online at https://doi.org/10.1063/1.4964760) - Designing 3D topological insulators by 2D-Xene (X = Ge, Sn) sheet functionalization in GaGeTe-type structures. J. Mater. Chem. C 2017, 5, 4752 – 4762
F. Pielnhofer, T. V. Menshchikova, I. P. Rusinov, A. Zeugner, I. Yu. Sklyadneva, R. Held, K.-P. Bohnen, P. Golub, A. I. Baranov, E. V. Chulkov, A. Pfitzner, M. Ruck, A. Isaeva
(See online at https://doi.org/10.1039/c7tc00390k) - Evolution of Real Space Electron Sharing Indices During Mott Transition in Hydrogen Lattices, Theor. Chem. Acc. 2017, 136, 96
A. I. Baranov, A. Martin Pendas
(See online at https://doi.org/10.1007/s00214-017-2125-8) - Synthesis of a Cu-Filled Rh17S15 Framework: Microwave Polyol Process Versus High-Temperature Route, Inorg. Chem. 2017, 56, 11513-11523
M. Roslova, P. Golub, L. Opherden, A. Ovchinnikov, M. Uhlarz, A. I. Baranov, Y. Prots, A. Isaeva, M. Coduri, T. Herrmannsdörfer, J. Wosnitza, T. Doert, M. Ruck
(See online at https://doi.org/10.1021/acs.inorgchem.7b01102)
