QTAIM method for accelerated prediction of band gaps in perovskites

Syzgantseva, Maria A.; Syzgantseva, Olga A.

doi:10.1007/s00214-019-2445-y

Cited by 6 publications

(6 citation statements)

References 59 publications

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“…Importantly, the same tendency is observed when the extent of conjugation in the organic ligand is increased: the band gap of an MOF is narrowing, which means lifting up the VB edge and shifting down the CB edge. This observation also supports the idea to use electron density on a ligand as a descriptor to assess the ionization potentials and electron affinities of MOFs …”

Section: Correlations Between the Electronic Structure Of A Ligand An...supporting

confidence: 80%

“…With this respect, the Pearson hardness and softness criteria can be suitable to predict the ionization potentials and electron affinities of MOFs . Precisely, the more electron density is present on a moiety, the easier it will be to detach an electron (the smaller is the ionization potential) …”

Section: Correlations Between the Electronic Structure Of A Ligand An...mentioning

confidence: 99%

“…However, qualitatively, the trend is in line with chemical hardness and softness of side groups: more soft ones lead to smaller IP in MOF with a ligand-centered valence band. Softer side groups increase the amount of electron density in the benzene ring, implying that the density can be used as a descriptor 55 to determine IP and EA in MOFs. Besides, introducing side groups in MOFs also modifies their acidobasic properties that is essential for lowering the reaction barriers of some crucial intermediate steps in redox reactions.…”

Section: Correlations Between the Electronic Structure Of A Ligand An...mentioning

confidence: 99%

“…This observation also supports the idea to use electron density on a ligand as a descriptor to assess the ionization potentials and electron affinities of MOFs. 55 The electron-donating capacity can be increased using heterocycles, where N, S, and possibly O are present as heteroatoms. Particularly interesting are thiazole compounds, containing N and S simultaneously, which are well known to have low ionization potentials.…”

Section: Correlations Between the Electronic Structure Of A Ligand An...mentioning

confidence: 99%

“…56 Precisely, the more electron density is present on a moiety, the easier it will be to detach an electron (the smaller is the ionization potential). 55…”

Section: Correlations Between the Electronic Structure Of A Ligand An...mentioning

confidence: 99%

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Band Alignment as the Method for Modifying Electronic Structure of Metal−Organic Frameworks

Syzgantseva

Stepanov

Syzgantseva

2020

ACS Appl. Mater. Interfaces

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Electronic-level ordering in metal–organic frameworks (MOFs) is a route to modulate their electronic properties such as optical absorption, band alignment, work function, charge separation, charge carrier lifetimes, and ground- or excited-state conductivity. A systematic application of this approach requires the knowledge on how a MOF chemical composition affects its electronic structure. In this work, the fundamental principles for selecting MOF components to achieve targeted level alignment are considered. Correlations between the electronic parameters of building blocks and MOF band structure are analyzed. The factors affecting the energy position of constituents are discussed. In particular, the impact of the chemical composition of ligands, including the structure of its scaffold and side groups, on their energy positions in MOFs is addressed. Besides, the effect of the choice of reference potential and surface termination on the band alignment is investigated. The performance of several density functionals in the computation of absolute band positions is assessed. Finally, general principles for the modification of the MOF electronic structure are formulated and the routes to achieve an appropriate band alignment with carrier-transporting materials, co-catalysts, and redox reaction potentials are suggested.

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Section: Correlations Between the Electronic Structure Of A Ligand An...supporting

confidence: 80%

Section: Correlations Between the Electronic Structure Of A Ligand An...mentioning

confidence: 99%

Section: Correlations Between the Electronic Structure Of A Ligand An...mentioning

confidence: 99%

Section: Correlations Between the Electronic Structure Of A Ligand An...mentioning

confidence: 99%

“…56 Precisely, the more electron density is present on a moiety, the easier it will be to detach an electron (the smaller is the ionization potential). 55…”

Section: Correlations Between the Electronic Structure Of A Ligand An...mentioning

confidence: 99%

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