Insights into the role of D-A-π-A type pro-aromatic organic dyes with thieno[3,4-b]pyrazine as A acceptor group into dye-sensitized solar-cells. A TD-DFT/periodic DFT study

Katherine Paredes-Gil, Dayán Páez-Hernández, Ramiro Arratia-Pérez, Fernando Mendizábal

Resultado de la investigación: Article

Resumen

Time-dependent density functional theory (TD-DFT)/periodic DFT calculations were performed to determine the role of pro-aromatic organic D-A-π-A type dyes (the NL1-NL17 family) with Thieno[3,4-b]pyrazine (Tpy) as A acceptor group into dye-sensitized solar-cells (DSSC). This work presents a discussion of the ground and excited states of these dyes along with the aromaticity analysis and the electron injection step using a dye@(TiO2)72 model. The results suggest that the pro-aromatic behavior increases from the thiophene ring to the pyrazine when an acceptor π-bridge such as phenyl is used. This strong pro-aromaticity is also reflected in the electron injection step, studied using a 3x2 3 layer (TiO2)72 slab model. The resulting adsorption energies (ΔEads and ΔGads) and the electron injection (ΔGinject) in the stablest coordination mode, Bid_CN_COOH, indicate that the redox reaction (Dye* ➔ Dye+ + e) is stronger and more spon than the adsorption reaction (Dye+ + TiO2 [+e] ➔ Dye@TiO2) in the electron injection. In this way, the highest efficiency of NL6 and NL12 is a consequence of the more significant pro-aromatic characteristics and the more spontaneous redox process. Finally, these NL dyes are promising in the molecular engineering of D-A-π-A metal-free types dyes.

Idioma originalEnglish
Número de artículoe26108
PublicaciónInternational Journal of Quantum Chemistry
DOI
EstadoAccepted/In press - 1 ene 2019

Huella dactilar

pyrazines
Discrete Fourier transforms
Density functional theory
Coloring Agents
solar cells
dyes
density functional theory
Electron injection
injection
electrons
Pyrazines
thieno(3,4-b)pyrazine
Dye-sensitized solar cells
Adsorption
Thiophenes
Redox reactions
adsorption
Laser modes
Excited states
Ground state

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Citar esto

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title = "Insights into the role of D-A-π-A type pro-aromatic organic dyes with thieno[3,4-b]pyrazine as A acceptor group into dye-sensitized solar-cells. A TD-DFT/periodic DFT study",
abstract = "Time-dependent density functional theory (TD-DFT)/periodic DFT calculations were performed to determine the role of pro-aromatic organic D-A-π-A type dyes (the NL1-NL17 family) with Thieno[3,4-b]pyrazine (Tpy) as A acceptor group into dye-sensitized solar-cells (DSSC). This work presents a discussion of the ground and excited states of these dyes along with the aromaticity analysis and the electron injection step using a dye@(TiO2)72 model. The results suggest that the pro-aromatic behavior increases from the thiophene ring to the pyrazine when an acceptor π-bridge such as phenyl is used. This strong pro-aromaticity is also reflected in the electron injection step, studied using a 3x2 3 layer (TiO2)72 slab model. The resulting adsorption energies (ΔEads and ΔGads) and the electron injection (ΔGinject) in the stablest coordination mode, Bid_CN_COOH, indicate that the redox reaction (Dye* ➔ Dye+ + e−) is stronger and more spon than the adsorption reaction (Dye+ + TiO2 [+e−] ➔ Dye@TiO2) in the electron injection. In this way, the highest efficiency of NL6 and NL12 is a consequence of the more significant pro-aromatic characteristics and the more spontaneous redox process. Finally, these NL dyes are promising in the molecular engineering of D-A-π-A metal-free types dyes.",
keywords = "D-A-π-A dyes, metal-free organic dyes, pro-aromatic molecules, solar cell, TiO surface",
author = "Katherine Paredes-Gil and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Ramiro Arratia-P{\'e}rez and Fernando Mendiz{\'a}bal",
year = "2019",
month = "1",
day = "1",
doi = "10.1002/qua.26108",
language = "English",
journal = "International Journal of Quantum Chemistry",
issn = "0020-7608",
publisher = "John Wiley and Sons Inc.",

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T1 - Insights into the role of D-A-π-A type pro-aromatic organic dyes with thieno[3,4-b]pyrazine as A acceptor group into dye-sensitized solar-cells. A TD-DFT/periodic DFT study

AU - Paredes-Gil, Katherine

AU - Páez-Hernández, Dayán

AU - Arratia-Pérez, Ramiro

AU - Mendizábal, Fernando

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Time-dependent density functional theory (TD-DFT)/periodic DFT calculations were performed to determine the role of pro-aromatic organic D-A-π-A type dyes (the NL1-NL17 family) with Thieno[3,4-b]pyrazine (Tpy) as A acceptor group into dye-sensitized solar-cells (DSSC). This work presents a discussion of the ground and excited states of these dyes along with the aromaticity analysis and the electron injection step using a dye@(TiO2)72 model. The results suggest that the pro-aromatic behavior increases from the thiophene ring to the pyrazine when an acceptor π-bridge such as phenyl is used. This strong pro-aromaticity is also reflected in the electron injection step, studied using a 3x2 3 layer (TiO2)72 slab model. The resulting adsorption energies (ΔEads and ΔGads) and the electron injection (ΔGinject) in the stablest coordination mode, Bid_CN_COOH, indicate that the redox reaction (Dye* ➔ Dye+ + e−) is stronger and more spon than the adsorption reaction (Dye+ + TiO2 [+e−] ➔ Dye@TiO2) in the electron injection. In this way, the highest efficiency of NL6 and NL12 is a consequence of the more significant pro-aromatic characteristics and the more spontaneous redox process. Finally, these NL dyes are promising in the molecular engineering of D-A-π-A metal-free types dyes.

AB - Time-dependent density functional theory (TD-DFT)/periodic DFT calculations were performed to determine the role of pro-aromatic organic D-A-π-A type dyes (the NL1-NL17 family) with Thieno[3,4-b]pyrazine (Tpy) as A acceptor group into dye-sensitized solar-cells (DSSC). This work presents a discussion of the ground and excited states of these dyes along with the aromaticity analysis and the electron injection step using a dye@(TiO2)72 model. The results suggest that the pro-aromatic behavior increases from the thiophene ring to the pyrazine when an acceptor π-bridge such as phenyl is used. This strong pro-aromaticity is also reflected in the electron injection step, studied using a 3x2 3 layer (TiO2)72 slab model. The resulting adsorption energies (ΔEads and ΔGads) and the electron injection (ΔGinject) in the stablest coordination mode, Bid_CN_COOH, indicate that the redox reaction (Dye* ➔ Dye+ + e−) is stronger and more spon than the adsorption reaction (Dye+ + TiO2 [+e−] ➔ Dye@TiO2) in the electron injection. In this way, the highest efficiency of NL6 and NL12 is a consequence of the more significant pro-aromatic characteristics and the more spontaneous redox process. Finally, these NL dyes are promising in the molecular engineering of D-A-π-A metal-free types dyes.

KW - D-A-π-A dyes

KW - metal-free organic dyes

KW - pro-aromatic molecules

KW - solar cell

KW - TiO surface

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