Computational Modelling — Microscopic Insights into Cation-Coupled Electron Hopping Transport in a Metal-Organic Framework

3 measurement groups · 19 results

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

DFT geometry optimisation and spin-density calculation (Jaguar 11.0; B3LYP-D3/LACVP**)

Density functional theory

Li+, K+, and TBA+ two-linker DFT cluster models · Model

Zr6 cluster with two NDI linkers; Li+, K+ or TBA+ counterion; PBF DMF solvation for spin density; BHandHLYP and omegaB97X checks.

Atmosphere: implicit DMF solvation model for spin-density calculations
Geometry: single cluster model with terminal COOH carbon positions restrained
Context: model system
Measurement source: 18 · DFT setup for single cluster with two linkers · Figure 8

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
O-O distance in K+ DFT model	4.2 A	—	—	Text Exact Reported	5917 · Computational Studies
K natural atomic charge	0.95	—	—	Text Exact Reported	5917 · Computational Studies
K+-O distance in DFT model, first contact	2.6 A	—	—	Text Exact Reported	5917 · Computational Studies
K+-O distance in DFT model, second contact	2.7 A	—	—	Text Exact Reported	5917 · Computational Studies
O-O distance in bridging Li+ DFT model	3.5 A	—	—	Text Exact Reported	5917 · Computational Studies
Li natural atomic charge	0.90	—	—	Text Exact Reported	5917 · Computational Studies
Li+-O distance in bridging Li+ DFT model	1.8 A to each oxygen	—	—	Text Rounded Reported	5917 · Computational Studies
Li+-bridged spin density localisation	spin delocalized over the two NDI linkers	—	—	Text Qualitative	5917 · Computational Studies · Figure 8
O-Li-O angle in bridging Li+ DFT model	161 degrees	—	—	Text Exact Reported	5917 · Computational Studies
TBA+ spin density localisation	spin localized on fragment close to cation	—	—	Text Qualitative	5917 · Computational Studies · Figure 8

molecular dynamics with AMBER16/AmberTools and GAFF2/RESP parameters

Molecular dynamics

reduced Zr(dcphOH-NDI) periodic MD model with Li+, K+, or TBA+ · Model

Fully reduced periodic Zr(dcphOH-NDI) model solvated in DMF or THF boxes, neutralised with Li+, K+ or TBA+; NVT heating to 300 K, NPT equilibration and production.

Temperature: 300
Atmosphere: computational periodic solvent box
Geometry: initial box approximately 100 A x 90 A x 110 A; PBC
Context: model system
Measurement source: 13-16 · Molecular Dynamics and Simulation Methods · Figures S10-S14, S16

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Li+ and K+ association time with reduced NDI linkers	less than 2 ns	—	—	Text Approximate	15 · Computational Studies
productive NPT MD time for one-linker systems	5 ns	—	—	Text Exact Reported	15 · Computational Studies
productive NPT MD time for UiO-NDI/PIZOF model	30 ns	—	—	Text Exact Reported	15 · Computational Studies
TBA+ association time with reduced NDI linkers	~10 ns	—	—	Text Approximate	15 · Computational Studies
RMSD solvent trend	cations move much faster in DMF compared to THF	—	—	Caption Qualitative	18 · Simulation Results and Discussion · Figure S16

steered MD, umbrella sampling and WHAM PMF analysis

Molecular dynamics

reduced Zr(dcphOH-NDI) periodic MD model with Li+, K+, or TBA+ · Model

One-linker reduced NDI/cation models in DMF or THF; 500 ps steered MD trajectories and 0.25 A umbrella windows for binding free energy profiles.

Temperature: 300
Atmosphere: computational DMF or THF solvent boxes
Geometry: isolated linker model with carboxylates replaced by hydrogen atoms
Context: model system
Measurement source: 15-17 · Molecular Dynamics and Simulation Methods · Figure S15

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
K+ dissociation free energy barrier in DMF	3.0 kcal/mol	—	—	Text Rounded Reported	17 · Computational Studies
K+ dissociation free energy barrier in THF	5.0 kcal/mol	—	—	Text Rounded Reported	17 · Computational Studies
Li+ dissociation free energy barrier in DMF	about 5.2 kcal/mol	—	—	Text Approximate	17 · Computational Studies
Li+ dissociation free energy barrier in THF	about 8.0 kcal/mol	—	—	Text Approximate	17 · Computational Studies