Computational Modelling — Probing charge transfer characteristics in a donor-acceptor metal-organic framework by Raman spectroelectrochemistry and pressure-dependence studies

2 measurement groups · 5 results

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

periodic DFT band structure; PBE and PBE0 functionals; all-electron TZVP basis; Crystal14

Density functional theory

periodic [(Zn(DMF))2(TTFTC)(DPNI)] DFT model · Model

Optimised MOF; 40 k-points Monkhorst-Pack mesh; band structure from high-symmetry points and 100 k-points interpolation.

Context: periodic pristine MOF model
Measurement source: p003-p004 / journal pages 25774-25775 · Band structure calculations; Results and discussion · Fig. S6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
direct band gap from PBE	0.4 eV	—	—	Text Exact Reported	p004 / journal page 25775 · Results and discussion · Fig. S6
indirect band gap from PBE0Marked as a best value within this paper	1.58 eV	—	—	Text Exact Reported	p004 / journal page 25775 · Results and discussion · Fig. S6
primary charge-transport mechanism	hole transport is the primary mechanism for charge migration	—	—	Text Qualitative	p005 / journal page 25776 · Results and discussion · Fig. S6

B3-LYP/6-31+G(d,p) Mulliken charge analysis on (TTFTC)(DPNI) model

(TTFTC)(DPNI) discrete computational model · Model

Geometry of (TTFTC)(DPNI) extracted from MOF crystal structure; discrete TTFTC and DPNI molecules optimised; harmonic frequency analysis with 0.9648 scale factor.

Context: discrete donor-acceptor model
Measurement source: p003-p005 / journal pages 25774-25776 · Density functional theory (DFT) calculations; In situ Raman spectroelectrochemistry · Scheme 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
DFT-predicted charge transfer in neutral TTFTC-DPNI complex	0.6 e-	—	—	Text Exact Reported	p005 / journal page 25776 · In situ Raman spectroelectrochemistry · Scheme 1
DFT-predicted charge transfer after oxidation	0.2 e-	—	—	Text Exact Reported	p007 / journal page 25778 · Conclusions · Scheme 1