Band Gaps of Perovskites

For machine learning

A and B(I) Elements
B(III) Elements
• In transition metal the d-d charge fluctuations (Coulomb and
Exchange) are suppressed because large energy involved. (Mott-
Hubbard theory)
• Late transition metal and high spin Mn2+ and Fe3+ compound
because of the exchange. (7-10 eV) Leads to Superexchange
• Confirm the usage of spin only Hamiltonian and Goodenough-
Kanamori rule
• Ti and V: Band Gap is d-d gap
• Co, Ni, Cu: Charge transfer type (related to electronegativity of
anion) 
• NiS, CuS, and CoS: Metallic (Charge transfer from anion valence Anderson Hamiltonian
band) Include V (charge transfer)
and U
• Frequently used approximation Treat as a cluster with
purely ionic ansatz

• If the bandgap is big and d-band dispersional widths are very small without translational
symmetry, cluster approximation is valid.

• Their method is follows:

• Calculate the ground state energy for n electron 
• Find the true ground state energy
• Create excitations and find gap
The band gap is given  by:

Where delta is the Hybridization energy

 Phase diagram:
Mott-Hubbard insulator (V203, Ti203, Cr203 and their halides), 
If U<delta it is Mott- Charge transfer insulator(CuC12, CuBr2, CuO,NiCl2, NiBr2, and
Hubbard in nature NiI2.), (AB) intermediate region (NiO, NiF2, CuF2), d-band metal
If U>delta it is charge (V203, Ti203, TiO, and Cr02), p-band metal (CuS, CuSe, and
transfer gap NiSe), Intermediate region with small gap
• Classification of the four mechanisms of gap formation with DFT
• In extreme ionic limit, the energy near Ef are degenerate with partial occupancy. There are two
points of view: Emerge from strong correlation without spatial symmetry breaking, or arise from
structural symmetry breaking
• Band theory which adopt zero moment by atoms basis, bound to produce zero gap
• In this study he minimized the total energy of the AFM and PM phases in supercell
representations that allow symmetry breaking, produces atomic displacements and other
symmetry-lowering modes and predict the correct trend for band gap without strong correlation
methodology
• Need to include: good interelectronic interaction (good exchange-correlation functional) and
structural degree of freedom that could be optimized.
Gapping mechanism 1: compounds forming closed subshells by octahedral breaking of atomic symmetry.

• The free ions Mn4+(d3) and Fe3+(d5) leads to partially filled degenerate
state but octahedral symmetry break the continous rotational d
symmetry. Making gap already at cubic level.  (CaMnO3and LaFeO3)
Gapping mechanism 2: compounds lifting electronic degeneracies due to octahedral rotations and those retaining
electronic degeneracies due to small or absent octahedral rotations

• For CaVO3, SrVO3, YTiO3 (d1), and LaMnO3(d4) due to a large A-to-B
cation size mismatch in ABO3, lowering the symmetry from cubic to
orthorhombic, resulting in bandgap. Although for LaMnO3 there is a
large Jahn Teller distorsion.
Gapping mechanism 3: compounds with two electrons in t2g levels.

• For LaVO3, due to pure steric effects, the O6 rotations are sufficiently

large to produce a new basis of orbitals, rendering a localized state in
the Pbnm symmetry. 
Gapping mechanism 4: compounds with unstable single local electronic occupation patterns
disproportionating into a double local environment

• For CaFeO3 and YNiO3, the Ni+3 is unstable and break to Ni2+ and Ni4+
at different sites. This more stable phase has insulating behavior
Why ionization potential of B1 has more effect
than B2
Direct and indirect bandgap for
A2BB'X6
High-throughput Computational Study of Halide Double Validation: A pencil-and-paper method for
                                                                                                                               
Perovskite Inorganic Compounds elucidating halidedouble perovskite band
Chem. Mater. 2019, 31,5392−5401 structures Chem. Sci.,2019,10,11041
                                                           

Another good reference:

R. Hoffmann,Solids and Surfaces: A Chemist's View of Bonding in
Extended Structures, Wiley-VCH, 1988
They concluded that there are 3 rules:​
1. If both B and B' metal orbitals contribute substantially, the extremum will be where
the halide SALCs around each site match the symmetry of the B and B' HOMOs (for the
VBM) or LUMOs (for the CBM).​
2. If only one B-site metal orbital is  involved in the band, the VBM will be at the kpoint
with SALCs that match thesymmetry of the HOMO and maximize the 90 X–X
antibonding interactions. CBM will be at the kpoint with SALCs that match the
symmetry of the LUMO l and maximize the 90 X–X bondingi nteractions.​
3. If no B-site metal orbitals participate in the valence band,the VBM will occur at the
kpoint that maximizes the number of d90 X–X antibonding interactions around both
sites.