Computational Modelling — Superexchange Charge Transport in Loaded Metal Organic Frameworks

6 measurement groups · 35 results

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

Quantum Patch / Loewdin orthogonalisation electronic couplings and Nelsen four-point reorganisation energies

Electrical conductivity

TCNQ/HKUST-1 computational model · Model

Electronic coupling matrix elements and reorganisation energies for HOMO and LUMO transport pathways in TCNQ/F4-TCNQ loaded HKUST-1.

Context: model parameter table for loaded HKUST-1 transport
Measurement source: 7087 · Results and Discussion · Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Activation energy for guest-guest hopping	67 meV	0.067 eV	—	Text Exact Reported	7087 · Results and Discussion · Table 1
F4-TCNQ HOMO reorganisation energy lambda	0.166 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
F4-TCNQ LUMO reorganisation energy lambda	0.271 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
MOF HOMO reorganisation energy lambda	0.664 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
MOF LUMO reorganisation energy lambda	0.580 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
TCNQ HOMO reorganisation energy lambda	0.129 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
TCNQ LUMO reorganisation energy lambda	0.266 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
LUMO F4-TCNQ-F4-TCNQ orthogonal coupling J	2.0 x 10^-8 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
LUMO F4-TCNQ-F4-TCNQ parallel coupling J	5.0 x 10^-9 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
LUMO F4-TCNQ-MOF coupling J	2.4 x 10^-3 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
LUMO MOF-MOF first-nearest-neighbour coupling J	5.7 x 10^-2 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
LUMO MOF-MOF second-nearest-neighbour coupling J	3.0 x 10^-5 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
LUMO TCNQ-MOF coupling J	1.4 x 10^-3 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
LUMO TCNQ-TCNQ orthogonal coupling J	1.7 x 10^-8 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1
LUMO TCNQ-TCNQ parallel coupling J	4.1 x 10^-9 eV	—	—	Table Exact Reported	7087 · Results and Discussion · Table 1

DFT geometry optimisation in Turbomole; B3-LYP XC functional, SV(P) basis, dispersion correction disp3

Density functional theory

F4-TCNQ/HKUST-1 computational model · Model

HKUST-1 subsets fixed during guest geometry optimisation; three binding configurations evaluated.

Context: F4-TCNQ/HKUST-1 model
Measurement source: S12 · 3.1 Calculation of the binding mechanism · Figure S9

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
F4-TCNQ binding energy, configuration aMarked as a best value within this paper	-1.84 eV per molecule in SI; main text says -1.82 eV	—	main/SI discrepancy: -1.82 vs -1.84 eV	Text Rounded Reported	S12 · 3.1 Calculation of the binding mechanism · Figure S9
Energy advantage of preferred F4-TCNQ configuration	0.66 eV	—	—	Caption Exact Reported	7087 · Results and Discussion · Figure 2
F4-TCNQ binding energy, configuration b	-0.91 eV per molecule	—	—	Text Exact Reported	S12 · 3.1 Calculation of the binding mechanism · Figure S9
F4-TCNQ binding energy, configuration c	-1.18 eV per molecule	—	—	Text Exact Reported	S12 · 3.1 Calculation of the binding mechanism · Figure S9

DFT geometry optimisation in Turbomole; B3-LYP XC functional, SV(P) basis, dispersion correction disp3

Density functional theory

TCNQ/HKUST-1 computational model · Model

HKUST-1 subsets fixed during guest geometry optimisation; three binding configurations evaluated.

Context: TCNQ/HKUST-1 model
Measurement source: S12 · 3.1 Calculation of the binding mechanism · Figure S9

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
TCNQ binding energy, configuration aMarked as a best value within this paper	-1.97 eV per molecule	—	—	Text Exact Reported	S12 · 3.1 Calculation of the binding mechanism · Figure S9
Energy advantage of preferred TCNQ configuration	0.72 eV	—	—	Caption Exact Reported	7087 · Results and Discussion · Figure 2
TCNQ binding energy, configuration b	-0.99 eV per molecule	—	—	Text Exact Reported	S12 · 3.1 Calculation of the binding mechanism · Figure S9
TCNQ binding energy, configuration c	-1.25 eV per molecule	—	—	Text Exact Reported	S12 · 3.1 Calculation of the binding mechanism · Figure S9

Injection-current model fitted to experimental current densities and KMC mobility

Pristine HKUST-1 SURMOF, 5 spray cycles · Thin Film

Device thicknesses 44.7 nm for pristine and F4-TCNQ-loaded MOF and 33.0 nm for TCNQ-loaded MOF; loaded/pristine current-density ratios averaged.

Geometry: Hg-drop vertical junction data converted for injection model
Context: experimental-model comparison for pristine and guest-loaded SURMOFs
Measurement source: S16 · 3.6 Model for injection current · Figure 6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Inferred LUMO-level difference between pristine and loaded MOF	around 0.6 eV	—	around	Text Approximate	7091 · Results and Discussion · Figure 6
F4-TCNQ mobility-curve intersection / inferred LUMO difference	approximately 0.62 eV	—	approximately	Caption Approximate	7091 · Results and Discussion · Figure 6
TCNQ mobility-curve intersection / inferred LUMO difference	approximately 0.71 eV	—	approximately	Caption Approximate	7091 · Results and Discussion · Figure 6
Difference in injection barriers between F4-TCNQ- and TCNQ-loaded MOF	roughly 0.1 eV	—	roughly	Text Approximate	7091 · Results and Discussion · Figure 6
KMC mobility of empty HKUST-1 used in injection model	1.25 x 10^-3 cm2/Vs	—	—	Text Exact Reported	S16 · 3.6 Model for injection current · Figure 6

Marcus rates plus kinetic Monte Carlo simulations

TCNQ/HKUST-1 computational model · Model

Five configurational disorder models; ten independent KMC simulations per model; 20 electrons injected; applied external electric field 0.035 V/nm.

Geometry: bulk KMC model
Context: electron transport in guest-loaded HKUST-1
Measurement source: S15-S16 · 3.5 Kinetic Monte Carlo · Figure 3; Figure 6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Direct-process activation energy when DeltaEgh > 0.4 eV	Ea is much larger than 0.42 eV	—	lower-bound statement	Text Approximate	7087 · Results and Discussion · Figure S11
Estimated F4-TCNQ LUMO shift relative to TCNQ	0.6 eV	—	estimated at least 0.6 eV	Caption Approximate	7088 · Results and Discussion · Figure 3c
Applied field in KMC simulations	0.035 V/nm	—	—	Text Exact Reported	S16 · 3.5 Kinetic Monte Carlo
Electron mobility enhancement from superexchange	up to 5 orders of magnitude larger than first-order processes	—	—	Caption Approximate	7088 · Results and Discussion · Figure 3c
Approximate loading/percolation threshold for qualitative guest difference	~35% of the sites	0.35 fraction of sites	approximately	Text Approximate	7091 · Results and Discussion
Estimated guest-host site energy difference threshold	DeltaEgh > 0.4 eV for both guest molecules	—	treated as a parameter due to DFT uncertainty	Text Approximate	7087 · Results and Discussion · Figure 3

Marcus rates plus kinetic Monte Carlo simulations for holes

TCNQ/HKUST-1 computational model · Model

Hole hopping rates and mobilities calculated analogously to electron case; compared with pristine HKUST-1 mobility.

Geometry: bulk KMC model
Context: hole transport in guest-loaded HKUST-1
Measurement source: S16-S17 · 3.7 Hole transport simulations · Figure 3d,e

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Maximum hole mobility increase upon loading	up to one order of magnitude only for DeltaE close to zero	—	qualitative energy-window statement	Caption Approximate	7088 · Results and Discussion · Figure 3e