Computational Modelling — Solid-State Electrochemical Carbon Dioxide Capture by Conductive Metal-Organic Framework Incorporating Nickel Bis(diimine) Units

Measurement evidence

Computational Modelling

Solid-State Electrochemical Carbon Dioxide Capture by Conductive Metal-Organic Framework Incorporating Nickel Bis(diimine) Units · Liu J., Yang M., Zhou X. et al. · Journal of the American Chemical Society · 2024 · 33093-33103

1 measurement group · 18 results

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

DFT charge, ESP and free-energy calculations

Density functional theory

Ni3(HITP)2 DFT model set · Model

Ni(DIB)2: Gaussian 16, B3LYP/def2-SVP with SMD; TD-SCF 6-311G++(d,p). Ni3(HITP)2: Dmol3, GGA-PBE, DN basis, DSPP core treatment.

Atmosphere: computational
Geometry: Molecular and framework model systems
Context: mechanistic models for reduced and CO2-adduct states
Measurement source: S34-S40 · 12.4 Computation Details · Figures S38-S47; Tables S2-S3

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Frontier-orbital transition energy gap for [Ni(DIB)2-CO2]-	1.42 eV	—	—	Text Exact Reported	S35 · 12.4 Computation Details · Figure S38
Frontier-orbital transition energy gap for Ni(DIB)2	1.47 eV	—	—	Text Exact Reported	S35 · 12.4 Computation Details · Figure S38
Frontier-orbital transition energy gap for [Ni(DIB)2]-	1.45 eV	—	—	Text Exact Reported	S35 · 12.4 Computation Details · Figure S38
Average Mulliken charge on N in Ni3(HITP)2 N-COOH adduct	-0.648	—	—	Text Exact Reported	33100 · Mechanism of CO2 Capture · Figure 5f
Average Mulliken charge on N in Ni3(HITP)2 NH-CO2 adduct	-0.587	—	—	Text Exact Reported	33100 · Mechanism of CO2 Capture · Figure S43
Average Mulliken charge on N in reduced Ni3(HITP)2	-0.677	—	—	Text Exact Reported	33100 · Mechanism of CO2 Capture · Figure 5f
Mulliken charge on N in reduced Ni(DIB)2	-0.275	—	—	Text Exact Reported	33100 · Mechanism of CO2 Capture · Figure 5e
Ni3(HITP)2 NH-CO2 product free-energy penalty vs N-COOH	18.3 kJ mol-1	—	—	Figure Axis Rounded Reported	33099 · Mechanism of CO2 Capture · Figure 5h
Ni3(HITP)2 Ni-CO2 d-p product free-energy penalty vs N-COOH	544.6 kJ mol-1	—	—	Figure Axis Rounded Reported	33099 · Mechanism of CO2 Capture · Figure 5h
Calculated free energy G for Ni3(HITP)2 acid-base adduct	-3187.03743 Ha	—	—	SI Table Exact Reported	S41 · 12.4 Computation Details · Table S3
Calculated free energy G for Ni3(HITP)2 carbamate adduct	-3187.044397 Ha	—	—	SI Table Exact Reported	S41 · 12.4 Computation Details · Table S3
Calculated free energy G for Ni3(HITP)2 d-p adduct	-3186.837005 Ha	—	—	SI Table Exact Reported	S41 · 12.4 Computation Details · Table S3
Ni(DIB)2 NH-CO2 product free-energy penalty vs N-COOH	8.7 kJ mol-1	—	—	Text Exact Reported	33100 · Mechanism of CO2 Capture · Figure 5g; Table S2
Ni(DIB)2 Ni-CO2 product free-energy penalty vs N-COOH	45.4 kJ mol-1	—	—	Text Exact Reported	33100 · Mechanism of CO2 Capture · Figure 5g; Table S2
Calculated free energy G for Ni(DIB)2 acid-base adduct	-2379.652106 Ha	—	—	SI Table Exact Reported	S40 · 12.4 Computation Details · Table S2
Calculated free energy G for Ni(DIB)2 carbamate adduct	-2379.655401 Ha	—	—	SI Table Exact Reported	S40 · 12.4 Computation Details · Table S2
Calculated free energy G for Ni(DIB)2 d-p adduct	-2379.638125 Ha	—	—	SI Table Exact Reported	S40 · 12.4 Computation Details · Table S2
Frontier-orbital transition energy gap for 785 nm absorption peak	1.58 eV	—	—	Text Exact Reported	S35 · 12.4 Computation Details · Figure S38