Benchmark Investigation of SCC-DFTB against Standard and Hybrid DFT to Model Electronic Properties in Two-Dimensional MOFs for Thermoelectric Applications

: Mahmoudi Gahrouei Masoumeh, Vlastos Nikiphoros, D’Souza Ransell, Odogwu Emmanuel C., de Sousa Oliveira Laura

Publisher: American Chemical Society

: 2024

: Journal of Chemical Theory and Computation

: Journal of chemical theory and computation

: J Chem Theory Comput

: 20

: 9

: 3976

: 3992

: 1549-9618

: 1549-9626

DOI: https://doi.org/10.1021/acs.jctc.3c01405(external)

: https://pubs.acs.org/doi/10.1021/acs.jctc.3c01405(external)

Recent studies have shown that metal-organic frameworks (MOFs) have potential as thermoelectric materials, and the topic has received increasing attention. The main motivation for this project is to further our knowledge of thermoelectric properties in MOFs and find which available self-consistent-charge density functional tight binding (SCC-DFTB) method can best predict (at least trends in) the electronic properties of MOFs at a lower computational cost than standard density functional theory (DFT). In this work, the electronic properties of monolayer, serrated, AA-stacked, and/or AB-stacked Zn₃C₆O₆, Cd₃C₆O₆, Zn-NH-MOF─for which no previous calculations of thermoelectric performance exist─and Ni₃(HITP)₂ MOFs are modeled with DFT-PBE, DFT-HSE06, GFN1-xTB, GFN2-xTB, and DFTB-3ob/mio. The band structures, density of states, and their relative orbital contributions, as well as the electrical conductivity, Seebeck coefficient, and power factor, are compared across methods and geometries. Our results suggest that GFN-xTB is adequate to predict the MOFs' band structure shape and density of states but not band gap. Our calculations further indicate that Zn₃C₆O₆, Cd₃C₆O₆, and Zn-NH-MOF have higher power factor values than Ni₃(HITP)₂, one of the highest performing synthesized MOFs, and are therefore promising for thermoelectric applications.