Three-Dimensional Real Space Invariants, Obstructed Atomic Insulators and A New Principle for Active Catalytic Sites

Topologically trivial insulators come in two kinds: atomic, where the Wannier charge centers (WCCs) are localized on the atoms, and obstructed atomic, where the WCCs are located away from the atoms. The latter, which can exhibit interesting surface states and possibly have much larger band gaps than the topological insulators, have so far not been classified in three-dimensional (3D) crystalline materials. In this paper, we developed the 3D real space invariants (RSIs) for the 1651 Shubnikov space groups with the spin-orbit coupling and provide the full classification of 3D obstructed atomic insulators (OAIs) by the RSIs. We then apply the theory to the entire database of materials on the Topological Quantum Chemistry website and Topological Magnetic Materials website, obtaining all the OAIs so far existing in nature. We find that, out of the 34013 paramagnetic and 296 magnetic topologically trivial insulators, there are 3383 paramagnetic and 30 magnetic OAIs. All of them present a filling anomaly under certain open-boundary conditions and exhibit obstructed surface states (OSSs). We further refine the atomic insulator concept to obtain the orbital-selected OAIs (OOAIs), where the WCC of the system is located at a Wyckoff position occupied by an atom but forms a symmetric representation that does not belong to the outer-shell electrons of the given atom. In such a way, we obtain a further 121 OOAIs. Furthermore, we analyze the catalytic properties of one of the OAIs in a "proof of principle" experiment. By using the single crystal of 2H-MoS2 as a hydrogen evolution catalyst, we directly prove that the catalytic activities arise from the surfaces with OSSs. Additional potential applications of the 3D RSIs and OAIs in, for example, electrochemistry, asymmetric catalysis, superconductivity, and Josephson diode will be discussed.
Comment: 12+149 pages, 3+16 figures. The calculations of RSIs for all the 34013 ICSDs of topologically trivial insulators are available at https://www.topologicalquantumchemistry.fr/flatbands/. See also "Obstructed surface states as the origin of catalytic activity in inorganic heterogeneous catalysts", Guowei Li et al