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Electronic Structure and Optical Response of Zn‐Based Metal–Organic Frameworks
Author(s) -
Vrubel Ivan I.,
Senkevich Natalia Yu.,
Khramenkova Elena V.,
Polozkov Roman G.,
Shelykh Ivan A.
Publication year - 2018
Publication title -
advanced theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.068
H-Index - 17
ISSN - 2513-0390
DOI - 10.1002/adts.201800049
Subject(s) - time dependent density functional theory , density functional theory , exciton , electronic structure , homo/lumo , electron , materials science , molecular physics , physics , chemistry , condensed matter physics , computational chemistry , molecule , quantum mechanics
The results of theoretical investigation of the equilibrium spatial configuration, electronic structure, and optical properties of the Zn‐based metal–organic framework [{Zn 2 (TBAPy)(H 2 O) 2 }*3.5DEF] n are reported. The electronic structure is obtained in frameworks of the density‐functional theory (DFT) with BLYP and PBE exchange‐correlation functionals, and optical response is computed using time‐dependent density functional theory (TDDFT). It is shown that the formation of narrow LUMO and HOMO bands is provided by conjugated π‐electrons of the aromatic rings of the ligand. These bands have nontrivial pattern and contain regions of hyperbolic dispersion corresponding to highly anisotropic heavy fermions. Optical transitions between these bands result in the appearance of near‐threshold peaks in photoabsorption spectra. The structure of the bands prevents formation of the bright exciton states in the system, and thus optical response is governed by single particle excitations only.