TY - JOUR
T1 - Ab initio modeling of 2D layered organohalide lead perovskites
AU - Fraccarollo, Alberto
AU - Cantatore, Valentina
AU - Boschetto, Gabriele
AU - Marchese, Leonardo
AU - Cossi, Maurizio
N1 - Publisher Copyright:
© 2016 Author(s).
PY - 2016/4/28
Y1 - 2016/4/28
N2 - A number of 2D layered perovskites A2PbI4 and BPbI4, with A and B mono- and divalent ammonium and imidazolium cations, have been modeled with different theoretical methods. The periodic structures have been optimized (both in monoclinic and in triclinic systems, corresponding to eclipsed and staggered arrangements of the inorganic layers) at the DFT level, with hybrid functionals, Gaussian-type orbitals and dispersion energy corrections. With the same methods, the various contributions to the solid stabilization energy have been discussed, separating electrostatic and dispersion energies, organic-organic intralayer interactions and H-bonding effects, when applicable. Then the electronic band gaps have been computed with plane waves, at the DFT level with scalar and full relativistic potentials, and including the correlation energy through the GW approximation. Spin orbit coupling and GW effects have been combined in an additive scheme, validated by comparing the computed gap with well known experimental and theoretical results for a model system. Finally, various contributions to the computed band gaps have been discussed on some of the studied systems, by varying some geometrical parameters and by substituting one cation in another's place.
AB - A number of 2D layered perovskites A2PbI4 and BPbI4, with A and B mono- and divalent ammonium and imidazolium cations, have been modeled with different theoretical methods. The periodic structures have been optimized (both in monoclinic and in triclinic systems, corresponding to eclipsed and staggered arrangements of the inorganic layers) at the DFT level, with hybrid functionals, Gaussian-type orbitals and dispersion energy corrections. With the same methods, the various contributions to the solid stabilization energy have been discussed, separating electrostatic and dispersion energies, organic-organic intralayer interactions and H-bonding effects, when applicable. Then the electronic band gaps have been computed with plane waves, at the DFT level with scalar and full relativistic potentials, and including the correlation energy through the GW approximation. Spin orbit coupling and GW effects have been combined in an additive scheme, validated by comparing the computed gap with well known experimental and theoretical results for a model system. Finally, various contributions to the computed band gaps have been discussed on some of the studied systems, by varying some geometrical parameters and by substituting one cation in another's place.
UR - http://www.scopus.com/inward/record.url?scp=84967185954&partnerID=8YFLogxK
U2 - 10.1063/1.4947305
DO - 10.1063/1.4947305
M3 - Article
SN - 0021-9606
VL - 144
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 16
M1 - 164701
ER -