10. DFT study of anthocyanidin and anthocyanin pigments for Dye-Sensitized Solar Cells: Electron injecting from the excited states and adsorption onto TiO2 (anatase) surface
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Emildo Marcano
Abstract
We explored, the absorption spectra, excited states and electronic injection parameters of anthocyanidin and anthocyanin pigments using the level of theory (TD)CAM-B3LYP/6-31+G(d,p). For the most isolated dyes, the distribution pattern of HOMO and LUMO spreads over the whole molecules, which lead an efficient electronic delocalization. The calculated light harvesting efficiencies (LHEs) are all near unity. Methoxy group in peonidin molecule lead the largest oscillator strength and LHE. The presence of water lead a higher spontaneous electronic inject process, with ΔGinject average of -1.14 eV. The ΔGinject order is peonidin < delphinidin < cyanin < cyanidin. Similarly, the adsorption energies (Eads) onto anatase surface model were obtained from level of theory GGA(PBE)/DNP. Eads of anthocyanin-(TiO2)30 complex was calculated to be from 17 to 24 eV, indicating both, the strong interactions between the dyes and the anatase (TiO2) surface and stronger electronic coupling strengths of the anthocyanin-(TiO2)30 complex, which corresponded to higher observed η. The HOMO and LUMO shape showed the electrons delocalized predominantly on the anthocyanin structure while the LUMO + 1 shape is localized into the (TiO2)30 surface. Therefore, we expected a electronic injection from HOMO to LUMO + 1 in the anthocyanin-(TiO2)30 adsorption complex, after the light absorption.
Abstract
We explored, the absorption spectra, excited states and electronic injection parameters of anthocyanidin and anthocyanin pigments using the level of theory (TD)CAM-B3LYP/6-31+G(d,p). For the most isolated dyes, the distribution pattern of HOMO and LUMO spreads over the whole molecules, which lead an efficient electronic delocalization. The calculated light harvesting efficiencies (LHEs) are all near unity. Methoxy group in peonidin molecule lead the largest oscillator strength and LHE. The presence of water lead a higher spontaneous electronic inject process, with ΔGinject average of -1.14 eV. The ΔGinject order is peonidin < delphinidin < cyanin < cyanidin. Similarly, the adsorption energies (Eads) onto anatase surface model were obtained from level of theory GGA(PBE)/DNP. Eads of anthocyanin-(TiO2)30 complex was calculated to be from 17 to 24 eV, indicating both, the strong interactions between the dyes and the anatase (TiO2) surface and stronger electronic coupling strengths of the anthocyanin-(TiO2)30 complex, which corresponded to higher observed η. The HOMO and LUMO shape showed the electrons delocalized predominantly on the anthocyanin structure while the LUMO + 1 shape is localized into the (TiO2)30 surface. Therefore, we expected a electronic injection from HOMO to LUMO + 1 in the anthocyanin-(TiO2)30 adsorption complex, after the light absorption.
Chapters in this book
- Frontmatter i
- Preface of the Book of Proceedings of the Virtual Conference on Computational Science (VCCS-2016) v
- Contents vii
- List of contributing authors xi
- 1. Addressing the challenges of standalone multi-core simulations in molecular dynamics 1
- 2. Optical and magnetic properties of free-standing silicene, germanene and T-graphene system 23
- 3. Theoretical study of the electronic states of newly detected dications. Case of MgS2+ AND SiN2+ 71
- 4. Analytical Solution of Pantograph Equation with Incommensurate Delay 93
- 5. Computational chemistry applied to vibrational spectroscopy: A tool for characterization of nucleic acid bases and some of their 5-substituted derivatives 117
- 6. Mechanism of nucleophilic substitution reactions of 4-(4’-nitro)phenylnitrobenzofurazan ether with aniline in acetonitrile 153
- 7. Computational methods in preformulation study for pharmaceutical solid dosage forms of therapeutic proteins 163
- 8. Computational Investigation of Cationic, Anionic and Neutral Ag2AuN (N = 1–7) Nanoalloy Clusters 173
- 9. Evacuation simulation using Hybrid Space Discretisation and Application to Large Underground Rail Tunnel Station 191
- 10. DFT study of anthocyanidin and anthocyanin pigments for Dye-Sensitized Solar Cells: Electron injecting from the excited states and adsorption onto TiO2 (anatase) surface 205
- 11. Elemental Two-Dimensional Materials Beyond Graphene 219
- Index 229
Chapters in this book
- Frontmatter i
- Preface of the Book of Proceedings of the Virtual Conference on Computational Science (VCCS-2016) v
- Contents vii
- List of contributing authors xi
- 1. Addressing the challenges of standalone multi-core simulations in molecular dynamics 1
- 2. Optical and magnetic properties of free-standing silicene, germanene and T-graphene system 23
- 3. Theoretical study of the electronic states of newly detected dications. Case of MgS2+ AND SiN2+ 71
- 4. Analytical Solution of Pantograph Equation with Incommensurate Delay 93
- 5. Computational chemistry applied to vibrational spectroscopy: A tool for characterization of nucleic acid bases and some of their 5-substituted derivatives 117
- 6. Mechanism of nucleophilic substitution reactions of 4-(4’-nitro)phenylnitrobenzofurazan ether with aniline in acetonitrile 153
- 7. Computational methods in preformulation study for pharmaceutical solid dosage forms of therapeutic proteins 163
- 8. Computational Investigation of Cationic, Anionic and Neutral Ag2AuN (N = 1–7) Nanoalloy Clusters 173
- 9. Evacuation simulation using Hybrid Space Discretisation and Application to Large Underground Rail Tunnel Station 191
- 10. DFT study of anthocyanidin and anthocyanin pigments for Dye-Sensitized Solar Cells: Electron injecting from the excited states and adsorption onto TiO2 (anatase) surface 205
- 11. Elemental Two-Dimensional Materials Beyond Graphene 219
- Index 229
