Computational Modelling — Ligand-Mediated Hydrogenic Defects in Two-Dimensional Electrically Conductive Metal-Organic Frameworks

11 measurement groups · 30 results

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

DFT electronic band-structure calculation.

Density functional theory

Ni3(HIB)2H single interstitial-hydrogen models · Model

Monolayer Ni3(HIB)2H and Ni3(HIB)2H2 band structures for H+, H-, H*, and 2H* interstitial configurations.

Geometry: Computed Gamma-K-M path.
Context: Hydrogen-defective model system.
Measurement source: SI p.6 · Figure S4 caption · Figure S4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
*Ni3(HIB)2H2 2H configuration 1 band gap**	Eg = 0.69 eV	—	—	Figure Axis Rounded Reported	SI p.6 · Figure S4 · Figure S4b
*Ni3(HIB)2H2 2H configuration 1 relative energy**	Erel = 0.23 kcal/mol	—	—	Figure Axis Rounded Reported	SI p.6 · Figure S4 · Figure S4b
*Ni3(HIB)2H2 2H configuration 2 band gap**	Eg = 0.76 eV	—	—	Figure Axis Rounded Reported	SI p.6 · Figure S4 · Figure S4b
*Ni3(HIB)2H2 2H configuration 2 relative energy**	Erel = 2.31 kcal/mol	—	—	Figure Axis Rounded Reported	SI p.6 · Figure S4 · Figure S4b
Ni3(HIB)2H2 monolayer electronic band gapMarked as a best value within this paper	Eg = 0.36 eV	—	—	Text Exact Reported	main p.3 / article p.11389 · Results and Discussion · Figure 3c
Ni3(HIB)2H H- interstitial band gap	Eg = 0.46 eV	—	—	Figure Axis Rounded Reported	SI p.6 · Figure S4 · Figure S4a
Ni3(HIB)2H H+ interstitial band gap	Eg = 0.27 eV	—	—	Figure Axis Rounded Reported	SI p.6 · Figure S4 · Figure S4a
*Ni3(HIB)2H H interstitial band gap**	Eg = 0.39 eV	—	—	Figure Axis Rounded Reported	SI p.6 · Figure S4 · Figure S4a

DFT point-defect formation energy calculation.

Density functional theory

Ni3(HIB)2H single interstitial-hydrogen models · Model

Interstitial hydrogen in Ni3(HIB)2 for H+, H-, H* and 2H* configurations under H-rich and H-poor chemical potentials.

Context: Hydrogen-defective model system.
Measurement source: main p.2 / article p.11388 · Results and Discussion · Figure 3b

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Double neutral interstitial-hydrogen thermodynamic favourability in Ni3(HIB)2Marked as a best value within this paper	2Hi / 2H* is even more negative and most favourable	—	—	Text Qualitative	main p.2 / article p.11388 · Results and Discussion · Figure 3b
Neutral interstitial-hydrogen formation enthalpy in Ni3(HIB)2	negative formation enthalpies; charge-neutral adatoms most favourable	—	—	Text Qualitative	main p.2 / article p.11388 · Results and Discussion · Figure 3b

DFT point-defect formation energy calculation.

Density functional theory

Ni3(HIB)2 hydrogen-vacancy model · Model

Hydrogen vacancy in Ni3(HIB)2 for charge states q = -1, 0, +1 under H-rich and H-poor chemical potentials.

Context: Hydrogen-defective model system.
Measurement source: main p.2 / article p.11388 · Results and Discussion · Figure 3a

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Charge-neutral hydrogen vacancy formation energy in Ni3(HIB)2	~0.9 eV	—	—	Text Approximate	main p.2 / article p.11388 · Results and Discussion · Figure 3a

DFT electronic band-structure calculation.

Density functional theory

vdW-stacked bulk Ni3(HITP)2H2 H*-reduced computational model · Model

Bulk vdW-stacked pristine and stoichiometric H*-reduced Ni3(HITP)2H2 models; in-plane Gamma-K-M-Gamma and out-of-plane Z-to-Gamma directions.

Geometry: Computed bulk reciprocal-space band paths.
Context: Pristine bulk model compared against hydrogen-defective bulk model.
Measurement source: main p.4 / article p.11390 · Results and Discussion · Figure 5d

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Bulk vdW-stacked Ni3(HITP)2H2 electronic band gapMarked as a best value within this paper	0.22 eV	—	—	Text Exact Reported	main p.4 / article p.11390 · Results and Discussion · Figure 5d

DFT electronic band-structure calculation.

Density functional theory

Ni3(HITP)2H single interstitial-hydrogen models · Model

Monolayer Ni3(HITP)2H and Ni3(HITP)2H2 band structures for H+, H-, H*, and 2H* interstitial configurations.

Geometry: Computed Gamma-K-M path.
Context: Hydrogen-defective model system.
Measurement source: SI p.7 · Figure S5 caption · Figure S5

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
*Ni3(HITP)2H2 2H configuration 1 band gap**	Eg = 0.46 eV	—	—	Figure Axis Rounded Reported	SI p.7 · Figure S5 · Figure S5b
*Ni3(HITP)2H2 2H configuration 1 relative energy**	Erel = 4.38 kcal/mol	—	—	Figure Axis Rounded Reported	SI p.7 · Figure S5 · Figure S5b
*Ni3(HITP)2H2 2H configuration 2 band gap**	Eg = 0.52 eV	—	—	Figure Axis Rounded Reported	SI p.7 · Figure S5 · Figure S5b
*Ni3(HITP)2H2 2H configuration 2 relative energy**	Erel = 3.92 kcal/mol	—	—	Figure Axis Rounded Reported	SI p.7 · Figure S5 · Figure S5b
*Ni3(HITP)2H2 2H configuration 3 band gap**	Eg = 0.51 eV	—	—	Figure Axis Rounded Reported	SI p.7 · Figure S5 · Figure S5b
Ni3(HITP)2H H- interstitial band gap	Eg = 0.15 eV	—	—	Figure Axis Rounded Reported	SI p.7 · Figure S5 · Figure S5a
Ni3(HITP)2H H+ interstitial band gap	Eg = 0.08 eV	—	—	Figure Axis Rounded Reported	SI p.7 · Figure S5 · Figure S5a
*Ni3(HITP)2H H interstitial band gap**	Eg = 0.29 eV	—	—	Figure Axis Rounded Reported	SI p.7 · Figure S5 · Figure S5a

DFT point-defect formation energy calculation.

Density functional theory

Ni3(HITP)2H single interstitial-hydrogen models · Model

Interstitial hydrogen in Ni3(HITP)2 for H+, H-, H*, and 2H* configurations.

Context: Hydrogen-defective model system.
Measurement source: main p.3 / article p.11389 · Results and Discussion · Figure 5

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
*Ni3(HITP)2 2H interstitial defect formation energy range**Marked as a best value within this paper	between -0.5 and -1.3 eV	—	range	Text Range	main p.3 / article p.11389 · Results and Discussion · Figure 5
Interstitial hydrogen formation energy sign in Ni3(HITP)2	negative formation energies in both H-rich and H-poor potentials	—	—	Text Qualitative	main p.3 / article p.11389 · Results and Discussion · Figure 5a,b

DFT phonon calculation.

Density functional theory

vdW-stacked bulk Ni3(HITP)2H2 H*-reduced computational model · Model

Gamma-point N-H stretching phonon modes for pristine Ni3(HITP)2 and defective Ni3(HITP)2H2.

Context: Pristine and hydrogen-defective computational models.
Measurement source: SI p.1 and p.3 · Computational Details; Tables S1-S2 · Tables S1-S2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Defective Ni3(HITP)2H2 NH2 stretching phonon rangeMarked as a best value within this paper	3344-3402 cm-1 for NH2 modes	—	range	SI Table Range	SI p.3 · Table S2 · Table S2
Defective Ni3(HITP)2H2 NH stretching phonon range	3464-3482 cm-1 for NH modes	—	range	SI Table Range	SI p.3 · Table S2 · Table S2
Pristine Ni3(HITP)2 N-H stretching phonon range	3464-3473 cm-1 for 12 N-H modes	—	range	SI Table Range	SI p.3 · Table S1 · Table S1

DFT point-defect formation energy calculation.

Density functional theory

Ni3(HITP)2 hydrogen-vacancy model · Model

Hydrogen vacancy in Ni3(HITP)2 under H-rich and H-poor chemical potentials.

Context: Hydrogen-defective model system.
Measurement source: main p.3 / article p.11389 · Results and Discussion · Figure 5a,b

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Charge-neutral hydrogen vacancy formation energy in Ni3(HITP)2 under H-poor conditions	~1.8 eV	—	—	Text Approximate	main p.3 / article p.11389 · Results and Discussion · Figure 5b
Charge-neutral hydrogen vacancy formation energy in Ni3(HITP)2 under H-rich conditions	~2.1 eV	—	—	Text Approximate	main p.3 / article p.11389 · Results and Discussion · Figure 5a

Periodic DFT in VASP using PAW, PBEsol geometry optimisation, HSEsol re-optimisation and band calculations.

Density functional theory

Pristine monolayer Ni3(HIB)2 computational model · Model

Plane-wave cutoff 500 eV; 20 A vacuum in z for monolayers; force convergence <0.01 eV/A; final energy change <1e-6 eV per atom; Gamma-centred k grids 4x4x1 for Ni3(HIB)2 and 2x2x1 for Ni3(HITP)2.

Context: General computational setup for pristine and defective model systems.
Measurement source: SI p.1 · Computational Details

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Defect-formation-energy cell-size sensitivity	within 0.03 eV	—	—	Text Rounded Reported	SI p.2 · Computational Details

DFT electronic band-structure calculation.

Density functional theory

Pristine monolayer Ni3(HIB)2 computational model · Model

Monolayer Ni3(HIB)2; in-plane Gamma-K-M path; HSEsol-level band structure after periodic optimisation.

Geometry: Computed reciprocal-space band path.
Context: Pristine model system.
Measurement source: main p.2 / article p.11388 · Results and Discussion · Figure 2b

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Pristine monolayer Ni3(HIB)2 electronic character	monolayer metal; two degenerate bands at Gamma diverging at K and M	—	—	Text Qualitative	main p.2 / article p.11388 · Results and Discussion · Figure 2b

DFT electronic band-structure calculation.

Density functional theory

Pristine monolayer Ni3(HITP)2 computational model · Model

Monolayer Ni3(HITP)2; in-plane Gamma-K-M path; HSEsol-level band structure after periodic optimisation.

Geometry: Computed reciprocal-space band path.
Context: Pristine model system.
Measurement source: main p.2 / article p.11388 · Results and Discussion · Figure 2a

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Pristine monolayer Ni3(HITP)2 in-plane electronic band gapMarked as a best value within this paper	Eg = 0.21 eV	—	—	Text Exact Reported	main p.2 / article p.11388 · Results and Discussion · Figure 2a