Computational Modelling — Dielectric relaxation processes, electronic structure, and band gap engineering of MFU-4-type metal-organic frameworks: Towards a rational design of semiconducting microporous materials

3 measurement groups · 12 results

Reported values remain attached to the sample, method, conditions, extraction quality and source location that produced them.

Gaussian09 cluster DFT using HSE hybrid functional and Def2-TZVP basis set

Density functional theory

Co5Cl4(HBBTA)6 Co-MFU-4 cluster model · Model

M(II)5Cl4(H-bbta)6 clusters with M = Zn2+ or Co2+; Co spin states S = 1.5, 4.5, 7.5 considered.

Temperature: 0
Atmosphere: in silico
Geometry: zero-dimensional Kuratowski cluster model
Context: cluster MFU-4 and Co-MFU-4 models
Measurement source: p011 · Experimental Section, Quantum Mechanical Investigations · Fig. 13 / Fig. S11-Fig. S14

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co5Cl4(HBBTA)6 Co-MFU-4 cluster HOMO-LUMO gapMarked as a best value within this paper	2.15 eV	—	—	Table Exact Reported	p008 · Cluster Calculations · Table 1 / Fig. 13
Co-MFU-4 cluster LUMO energy	-3.99 eV	—	—	Text Exact Reported	p009 · Cluster Calculations · Fig. 13
H2BBTA ligand HOMO-LUMO gap	3.07 eV	—	—	Text Exact Reported	p009 · Cluster Calculations · Fig. 13
Zn5Cl4(HBBTA)6 MFU-4 cluster HOMO-LUMO gapMarked as a best value within this paper	3.15 eV	—	—	Table Exact Reported	p008 · Cluster Calculations · Table 1 / Fig. 13
MFU-4 cluster LUMO energy	-2.99 eV	—	—	Text Exact Reported	p009 · Cluster Calculations · Fig. 13

Force-field molecular dynamics electrical poling/depolarisation simulations using UFF in GULP V4.0

Molecular dynamics

DMF@MFU-4 MD model · Model

Thermally equilibrated cells poled with 1.0 eV A^-1 electric field along c at 298 K for 20 ps, then relaxation sampled for 100 ps; DMF charges from COMPASS, MFU-4 charges from CASTEP/PBE.

Temperature: 298
Atmosphere: in silico
Geometry: periodic MD boxes
Context: DMF-loaded MFU-4 model compared with pure DMF and empty MFU-4
Measurement source: p015 · Electrical Poling Behaviour of DMF@MFU-4 · Fig. S15-Fig. S18

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
DMF@MFU-4 MD depolarisation relaxation timeMarked as a best value within this paper	tau = 6.6 ps	—	—	Text Exact Reported	p005 · Relaxation Dynamics · Fig. 7
Empty MFU-4 MD depolarisation	much faster depolarization; not fit by a single exponential decay	—	—	Text Qualitative	p005 · Relaxation Dynamics · Fig. 7 inset
Pure DMF MD depolarisation relaxation timeMarked as a best value within this paper	tau = 25.3 ps	—	—	Text Exact Reported	p005 · Relaxation Dynamics · Fig. 7

Periodic DFT using VASP 5.2.12 with PW91, PBE, and HSE functionals

Density functional theory

Periodic Co-MFU-4 unit-cell model · Model

Unit cells containing 204 atoms; PAW plane waves, 450 eV cutoff; HSE06 range-separation; Co-MFU-4 HSE with 700 bands and one k-point.

Temperature: 0
Atmosphere: in silico
Geometry: periodic unit cell model
Context: periodic MFU-4 and Co-MFU-4 models
Measurement source: p011 · Experimental Section, Quantum Mechanical Investigations · Table 1 / Table S1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-MFU-4 periodic HSE band gapMarked as a best value within this paper	2.63 eV	—	—	Table Exact Reported	p008 · Quantum Mechanical Calculations · Table 1
MFU-4 periodic HSE band gapMarked as a best value within this paper	3.43 eV	—	—	Table Exact Reported	p008 · Quantum Mechanical Calculations · Table 1
MFU-4 periodic PBE band gap	2.52 eV	—	—	SI Table Exact Reported	p005 · Benchmarking computational results · Table S1
MFU-4 periodic PW91 band gap	2.53 eV	—	—	SI Table Exact Reported	p005 · Benchmarking computational results · Table S1