Electron states of 2D metal-organic and covalent-organic honeycomb frameworks: ab initio results and a general fitting hamiltonian

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Universidade Federal de Minas Gerais

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Artigo de periódico

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We present a tight-binding model that allows a quantitative fitting of the ab initio band structure, near the Fermi energy, of several 2D metal–organic and covalent–organic honeycomb-like frameworks. The model is based on the kagome–honeycomb lattice, defined as the superposition of the named lattices. The full spectrum of the model Hamiltonian is analytically solvable in the case of one orbital per site and nearest-neighbor hopping, and at selected points of the Brillouin zone for hopping up to second neighbors. With proper choices of parameters and band occupation, the model describes five types of electronic structure within this class of materials. All five types are obtained in explicit fittings of the model to first-principles calculations of 2D frameworks. The model also permits the identification of crystallographic point group broken symmetries that lead to band gap openings in Cu3(HITP)2. Spin–orbit effects are also investigated in model and first-principles calculations of Ni3C12S12.

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Estrutura eletrônica, Teoria de grupos

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Electron states, Band structure, Covalent organic frameworks, First-principles calculations, Group theory

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https://pubs.acs.org/doi/10.1021/acs.jpcc.6b05081

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