Computational Modelling — Semiconducting properties of pyridyl appended linear dicarboxylate based coordination polymers: Theoretical prediction: Via DFT study

7 measurement groups · 29 results

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

DFT band structure and PDOS using CASTEP, GGA-PBE, norm-conserving pseudopotentials, Koelling-Harmon relativistic treatment, 600 eV cutoff, 1 x 1 x 1 Monkhorst-Pack k-mesh, Grimme dispersion; PDOS grid 3 x 3 x 2.

Density functional theory

Compound 1 DFT crystal model · Model

Atomic positions optimised with experimental lattice fixed; SCF tolerance 2 x 10^-6 eV per atom; conduction bands shifted by a +0.45 eV scissor operator.

Atmosphere: not_applicable
Geometry: periodic crystal model
Context: model system for pristine framework
Measurement source: main pp.2-3, article pp.271-272 · Computational details · Figs. 2-3

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Compound 1 direct band-gap path	Direct band gap from G branch to F point of BZ	—	—	Text Qualitative	main p.3, article p.272 · Electronic band gap measurement · Fig. 2
Compound 1 valence/conduction orbital assignment	Valence bands mainly dominated by adc and water p orbitals; conduction-band bottom mainly 4-phpy 2p orbitals; Cd contribution negligible near LUMO.	—	—	Text Qualitative	main p.4, article p.273 · Study of partial density of states (PDOS) · Figs. 3-4
Compound 1 DFT scissor operator shift	+0.45 eV	—	—	Text Exact Reported	main p.3, article p.272 · Computational details · Fig. 2

DFT band structure and PDOS using CASTEP, GGA-PBE, norm-conserving pseudopotentials, Koelling-Harmon relativistic treatment, 600 eV cutoff, 1 x 1 x 1 Monkhorst-Pack k-mesh, Grimme dispersion; PDOS grid 3 x 3 x 3.

Density functional theory

Compound 2 DFT crystal model · Model

Atomic positions optimised with experimental lattice fixed; SCF tolerance 2 x 10^-6 eV per atom; conduction bands shifted by a +1.40 eV scissor operator.

Atmosphere: not_applicable
Geometry: periodic crystal model
Context: model system for pristine framework
Measurement source: main pp.2-3, article pp.271-272 · Computational details · Figs. 2-3

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Compounds 2 and 3 principal direct band-gap paths	Direct band gaps principally in G to Z and G to F points of their BZ	—	—	Text Qualitative	main p.3, article p.272 · Electronic band gap measurement · Fig. 2
Compound 2 valence/conduction orbital assignment	Valence bands mainly dominated by adc and water p orbitals; conduction-band bottom mainly 4-phpy 2p orbitals; Zn contribution negligible near LUMO.	—	—	Text Qualitative	main p.4, article p.273 · Study of partial density of states (PDOS) · Figs. 3 and 5
Compound 2 DFT scissor operator shiftMarked as a best value within this paper	+1.4 eV	—	—	Text Exact Reported	main p.3, article p.272 · Computational details · Fig. 2

DFT band structure and PDOS using CASTEP, GGA-PBE, norm-conserving pseudopotentials, Koelling-Harmon relativistic treatment, 600 eV cutoff, 1 x 1 x 1 Monkhorst-Pack k-mesh, Grimme dispersion; PDOS grid 3 x 3 x 2.

Density functional theory

Compound 3 DFT crystal model · Model

Atomic positions optimised with experimental lattice fixed; SCF tolerance 2 x 10^-6 eV per atom; conduction bands shifted by a +0.60 eV scissor operator.

Atmosphere: not_applicable
Geometry: periodic crystal model
Context: model system for pristine framework
Measurement source: main pp.2-3, article pp.271-272 · Computational details · Figs. 2-3

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Compound 3 valence/conduction orbital assignmentMarked as a best value within this paper	Cu 3d orbitals and muconate 2p orbitals dominate the valence-band top and conduction-band bottom.	—	—	Text Qualitative	main p.6, article p.275 · Study of partial density of states (PDOS) · Figs. 3 and 6
Compound 3 DFT scissor operator shift	+0.6 eV	—	—	Text Exact Reported	main p.3, article p.272 · Computational details · Fig. 2

TD-DFT excited-state energy and geometry calculations implemented in CASTEP; Dmol3 molecular orbital starting calculations with DNP basis and PBE functional.

Density functional theory

Compound 3 DFT crystal model · Model

First two excited states calculated for compound 3; SI Table S2 reports ground-state, first-excited and second-excited geometrical measurements.

Atmosphere: not_applicable
Geometry: periodic crystal/model calculation
Context: model system for pristine framework
Measurement source: main p.3, article p.272 · Computational details · Table S2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Compound 3 excited-state Cu-ligand bond elongation	0.05-0.07 A elongation	—	—	Text Range	main p.7, article p.276 · Measurement of optical parameters · Table S2
Compound 3 first excited-state transition-energy reductionMarked as a best value within this paper	0.15 eV decrease	—	—	Text Exact Reported	main p.7, article p.276 · Measurement of optical parameters · Table S2
Compound 3 new excited-state Cu-O6 bond	new bond between Cu-O6 in the 1st and 2nd excited states	—	—	Text Qualitative	main p.7, article p.276 · Measurement of optical parameters · Table S2
Compound 3 Cu-N1 bond length in first excited state	Cu-N1: GS 2.07 A, 1st 2.12 A, 2nd 2.11 A	—	—	SI Table Exact Reported	SI p.5 · Table S2 · Table S2
Compound 3 Cu-N1 bond length in ground state	Cu-N1: GS 2.07 A, 1st 2.12 A, 2nd 2.11 A	—	—	SI Table Exact Reported	SI p.5 · Table S2 · Table S2
Compound 3 Cu-O1 bond length in first excited state	Cu-O1: GS 1.99 A, 1st 2.06 A, 2nd 2.04 A	—	—	SI Table Exact Reported	SI p.5 · Table S2 · Table S2
Compound 3 Cu-O1 bond length in ground state	Cu-O1: GS 1.99 A, 1st 2.06 A, 2nd 2.04 A	—	—	SI Table Exact Reported	SI p.5 · Table S2 · Table S2
Compound 3 Cu-O2 bond length in first excited state	Cu-O2: GS 2.01 A, 1st 2.06 A, 2nd 2.08 A	—	—	SI Table Exact Reported	SI p.5 · Table S2 · Table S2
Compound 3 Cu-O2 bond length in ground state	Cu-O2: GS 2.01 A, 1st 2.06 A, 2nd 2.08 A	—	—	SI Table Exact Reported	SI p.5 · Table S2 · Table S2
Compound 3 Cu-O6 bond length in first excited state	Cu-O6: no GS value, 1st 2.22 A, 2nd 2.23 A	—	—	SI Table Exact Reported	SI p.5 · Table S2 · Table S2
Compound 3 Cu-O6 bond length in second excited state	Cu-O6: no GS value, 1st 2.22 A, 2nd 2.23 A	—	—	SI Table Exact Reported	SI p.5 · Table S2 · Table S2

Computed optical conductivity sigma(omega) versus photon energy for polarised light directions.

Electrical conductivity

Compound 1 DFT crystal model · Model

Photon energy range 0-16 eV; plotted real and imaginary parts for compounds 1-3. Measurement row is attached to compound 1 model; result names specify compounds 1-3.

Atmosphere: not_applicable
Geometry: periodic crystal model
Context: model systems for pristine frameworks
Measurement source: main p.7, article p.276 · Measurement of optical parameters · Fig. 8

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Computed optical conductivity response under illumination	Optical conductivity behaviour is similar to dielectric constant; conductivity and photoconductivity increase as a consequence of photon absorption.	—	—	Text Qualitative	main p.6, article p.275 · Measurement of optical parameters · Fig. 8

Computed frequency-dependent dielectric function epsilon(omega) from band structures for plane-polarised light along (100), (010), and (001); 0.2 eV smearing.

Compound 1 DFT crystal model · Model

Photon energy range 0-16 eV; anisotropic dielectric components decomposed into x, y and z directions. Measurement row is attached to compound 1 model; result names specify compounds 1-3.

Atmosphere: not_applicable
Geometry: periodic crystal model
Context: model systems for pristine frameworks
Measurement source: main p.6, article p.275 · Dielectric function study · Fig. 7

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Compound 1 dielectric absorption range	3.4-8 eV	—	—	Text Range	main p.6, article p.275 · Dielectric function study · Fig. 7
Compound 1 epsilon_xx and epsilon_yy dielectric onset	epsilon_xx and epsilon_yy start at 3.8 eV	—	—	Text Rounded Reported	main p.6, article p.275 · Dielectric function study · Fig. 7
Compound 1 epsilon_zz dielectric onset	epsilon_zz starts at 3.5 eV	—	—	Text Rounded Reported	main p.6, article p.275 · Dielectric function study · Fig. 7
Compound 3 common dielectric component onset	all components started at 2.0 eV	—	—	Text Rounded Reported	main p.6, article p.275 · Dielectric function study · Fig. 7
Compound 3 dielectric peak energy 1	4.0 eV	—	—	Text Rounded Reported	main p.6, article p.275 · Dielectric function study · Fig. 7
Compound 3 dielectric peak energy 2	6.2 eV	—	—	Text Rounded Reported	main p.6, article p.275 · Dielectric function study · Fig. 7

TD-DFT excited-state energy and geometry calculations implemented in CASTEP; Dmol3 molecular orbital starting calculations with DNP basis and PBE functional.

Density functional theory

Compound 1 DFT crystal model · Model

First two excited states calculated for compound 1; SI Table S1 reports ground-state, first-excited and second-excited geometrical measurements.

Atmosphere: not_applicable
Geometry: periodic crystal/model calculation
Context: model systems for pristine frameworks
Measurement source: main p.3, article p.272 · Computational details · Tables S1-S2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Compound 1 first excited-state transition-energy reduction	0.04 eV drop	—	—	Text Exact Reported	main p.7, article p.276 · Measurement of optical parameters · Table S1
Compound 1 Cd-N2 bond length in second excited state	Cd-N2: GS 2.33 A, 1st 2.33 A, 2nd 2.37 A	—	—	SI Table Exact Reported	SI p.4 · Table S1 · Table S1
Compound 1 C13-C14-C17-C18 dihedral angle in second excited state	C13-C14-C17-C18: GS 18.8 deg, 1st 10.0 deg, 2nd 9.2 deg	—	—	SI Table Exact Reported	SI p.4 · Table S1 · Table S1