Computational Modelling — Beyond diffusion: ion and electron migration contribute to charge transport in redox-conducting metal-organic frameworks

2 measurement groups · 13 results

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

DFT molecular redox models · Model

Gaussian 16 Rev. C.02; B3LYP-D3/Def2TZVP; COSMO DMF; RRHO thermal corrections via SHERMO at 298.15 K and 1 atm

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
DFT-calculated Co(III)/Co(II) redox potential	+0.30 V versus SCE	—	—	Text Rounded Reported	p020 / SI page S20 · 4.2.3 DFT computational details
experimental lower bound for cross-exchange rate constant	k >= 10^2 M^-1 s^-1	—	lower bound	Calculated From Reported Approximate	p018 / SI page S18 · 4.2.1 Determining a lower bound for k using Damkohler numbers
Marcus/DFT cross-exchange rate constantMarked as a best value within this paper	k = 6 x 10^7 M^-1 s^-1	—	approximate calculation	Text Approximate	p019 / SI page S19 · 4.2.2 Marcus theory and DFT calculations
cross-exchange rate with reduced collision frequency scenario	k = 6 x 10^4 M^-1 s^-1	—	alternative scenario	Text Approximate	p019 / SI page S19 · 4.2.2 Marcus theory and DFT calculations
internal reorganisation energy for [Co(bpy)3] redox couple	lambda_int = 2.675 eV	—	—	SI Table Exact Reported	p021 / SI page S21 · 4.2.3 DFT computational details · energy table
internal reorganisation energy for NDI redox couple	lambda_int = 0.467 eV	—	—	SI Table Exact Reported	p021 / SI page S21 · 4.2.3 DFT computational details · energy table
standard potential difference for Marcus cross relation	Delta E0 = 0.8 V	—	—	Text Rounded Reported	p018 / SI page S18 · 4.2.2 Marcus theory and DFT calculations

analytical planar redox-film model · Model

Planar 1D redox film; migration and electric-field effects included; simulations varied mobile ion concentration and fitted catalytic CV

Geometry: 1D planar film of thickness df between electrode and solution interface
Context: model system based on Zn(NDI)@FTO
Measurement source: p015 / SI page S15 · 3.6 Computational details and model verification · Figure S2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
mobile ion excess parameter beta	beta = C0I/C0P = 0.5	—	—	SI Table Exact Reported	p023 / SI page S23 · 5.2 Governing dimensionless parameters · Table S2
acceptor excess parameter gamma	gamma = C0A/C0P = 0.036	—	—	SI Table Exact Reported	p023 / SI page S23 · 5.2 Governing dimensionless parameters · Table S2
surface electron-transfer Damkohler number	Lambda = 1.3	—	—	SI Table Exact Reported	p023 / SI page S23 · 5.2 Governing dimensionless parameters · Table S2
low-ion plateau-current enhancement from migration	factor of 3/2 (1.5-fold)	—	asymptotic limit	Calculated From Reported Exact Reported	p015 / SI page S15 · 3.5 Asymptotic approximation for the plateau current · Eq. S104-S105
simulated low-ion plateau current ratio at C0I/C0P = 0.2	approximately 1.25-1.3 i_pl/i_D	—	visual estimate from plot	Visual Estimate Approximate	p006 / journal page 5219 · Results and discussion · Fig. 3a
dimensionless Debye length theta	Theta = 4 x 10^-4	—	—	SI Table Exact Reported	p023 / SI page S23 · 5.2 Governing dimensionless parameters · Table S2