Electronic structure and optical properties calculation of Zn-porphyrin with N-annulated perylene adsorbed on TiO2 model for dye-sensitized solar cell applications

A DFT/TD-DFT study

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

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The current work scrutinizes the chemical behavior of a set of promissory dyes, the Zn-porphyrins with N-annulated Perylene, WW3m-WW8m, within the most important steps in the solar cell: photoexcitation, electron injection and dye regeneration. The photoexcitation step was studied through TD-DFT framework, finding that the most intense band in WW4m, WW6m-WW8m corresponds to the electronic transition of the frontier orbitals HOMO-LUMO. Among these, WW6m is highlighted, because the electronic density of the LUMO is localized over the anchoring group. Therefore, the presence of two ethynylene spacers in the WW6m porphyrin originate an enhancement in the light absorption. On the other hand, we analyze the electron injection modelling two (mono and bidentate) adsorbing modes in WW3m@TiO2-WW8m@TiO2 using DFT (B3LYP+D3) calculations. Adsorption energies show that WW3m@TiO2-WW8m@TiO2 are coordinated in bidentate mode. In this sense, to analyze the density of states (DOS) we found that WW6m@TiO2 present the narrowest band gap (1.53 eV), promoting an easy electron injection, which could explain the origin of the highest overall efficiency of the solar cell for this porphyrin. Finally, dye regeneration, was studied through the free energy associated, ΔGregen, the values are between −6.61 and −6.93 eV for WW3m@TiO2-WW8m@TiO2 showing that this step is spontaneous and similar in all porphyrins.

Original languageEnglish
Pages (from-to)514-527
Number of pages14
JournalComputational Materials Science
Volume126
DOIs
Publication statusPublished - 1 Jan 2017

Fingerprint

Perylene
Time-dependent Density Functional Theory
Porphyrin
Electron injection
TiO2
Porphyrins
Electronic Structure
Solar Cells
Dyes
Discrete Fourier transforms
porphyrins
Optical Properties
Electronic structure
Coloring Agents
Optical properties
Photoexcitation
solar cells
dyes
injection
electronic structure

Keywords

  • Computational studies
  • N-annulated perylene Zn-porphyrin
  • Solar cell
  • TiO model

ASJC Scopus subject areas

  • Computer Science(all)
  • Chemistry(all)
  • Materials Science(all)
  • Mechanics of Materials
  • Physics and Astronomy(all)
  • Computational Mathematics

Cite this

@article{1213a4b13dca4d42992d7c155a1c48fd,
title = "Electronic structure and optical properties calculation of Zn-porphyrin with N-annulated perylene adsorbed on TiO2 model for dye-sensitized solar cell applications: A DFT/TD-DFT study",
abstract = "The current work scrutinizes the chemical behavior of a set of promissory dyes, the Zn-porphyrins with N-annulated Perylene, WW3m-WW8m, within the most important steps in the solar cell: photoexcitation, electron injection and dye regeneration. The photoexcitation step was studied through TD-DFT framework, finding that the most intense band in WW4m, WW6m-WW8m corresponds to the electronic transition of the frontier orbitals HOMO-LUMO. Among these, WW6m is highlighted, because the electronic density of the LUMO is localized over the anchoring group. Therefore, the presence of two ethynylene spacers in the WW6m porphyrin originate an enhancement in the light absorption. On the other hand, we analyze the electron injection modelling two (mono and bidentate) adsorbing modes in WW3m@TiO2-WW8m@TiO2 using DFT (B3LYP+D3) calculations. Adsorption energies show that WW3m@TiO2-WW8m@TiO2 are coordinated in bidentate mode. In this sense, to analyze the density of states (DOS) we found that WW6m@TiO2 present the narrowest band gap (1.53 eV), promoting an easy electron injection, which could explain the origin of the highest overall efficiency of the solar cell for this porphyrin. Finally, dye regeneration, was studied through the free energy associated, ΔGregen, the values are between −6.61 and −6.93 eV for WW3m@TiO2-WW8m@TiO2 showing that this step is spontaneous and similar in all porphyrins.",
keywords = "Computational studies, N-annulated perylene Zn-porphyrin, Solar cell, TiO model",
author = "Katherine Paredes-Gil and Fernando Mendizabal and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Ramiro Arratia-P{\'e}rez",
year = "2017",
month = "1",
day = "1",
doi = "10.1016/j.commatsci.2016.09.042",
language = "English",
volume = "126",
pages = "514--527",
journal = "Computational Materials Science",
issn = "0927-0256",
publisher = "Elsevier",

}

TY - JOUR

T1 - Electronic structure and optical properties calculation of Zn-porphyrin with N-annulated perylene adsorbed on TiO2 model for dye-sensitized solar cell applications

T2 - A DFT/TD-DFT study

AU - Paredes-Gil, Katherine

AU - Mendizabal, Fernando

AU - Páez-Hernández, Dayán

AU - Arratia-Pérez, Ramiro

PY - 2017/1/1

Y1 - 2017/1/1

N2 - The current work scrutinizes the chemical behavior of a set of promissory dyes, the Zn-porphyrins with N-annulated Perylene, WW3m-WW8m, within the most important steps in the solar cell: photoexcitation, electron injection and dye regeneration. The photoexcitation step was studied through TD-DFT framework, finding that the most intense band in WW4m, WW6m-WW8m corresponds to the electronic transition of the frontier orbitals HOMO-LUMO. Among these, WW6m is highlighted, because the electronic density of the LUMO is localized over the anchoring group. Therefore, the presence of two ethynylene spacers in the WW6m porphyrin originate an enhancement in the light absorption. On the other hand, we analyze the electron injection modelling two (mono and bidentate) adsorbing modes in WW3m@TiO2-WW8m@TiO2 using DFT (B3LYP+D3) calculations. Adsorption energies show that WW3m@TiO2-WW8m@TiO2 are coordinated in bidentate mode. In this sense, to analyze the density of states (DOS) we found that WW6m@TiO2 present the narrowest band gap (1.53 eV), promoting an easy electron injection, which could explain the origin of the highest overall efficiency of the solar cell for this porphyrin. Finally, dye regeneration, was studied through the free energy associated, ΔGregen, the values are between −6.61 and −6.93 eV for WW3m@TiO2-WW8m@TiO2 showing that this step is spontaneous and similar in all porphyrins.

AB - The current work scrutinizes the chemical behavior of a set of promissory dyes, the Zn-porphyrins with N-annulated Perylene, WW3m-WW8m, within the most important steps in the solar cell: photoexcitation, electron injection and dye regeneration. The photoexcitation step was studied through TD-DFT framework, finding that the most intense band in WW4m, WW6m-WW8m corresponds to the electronic transition of the frontier orbitals HOMO-LUMO. Among these, WW6m is highlighted, because the electronic density of the LUMO is localized over the anchoring group. Therefore, the presence of two ethynylene spacers in the WW6m porphyrin originate an enhancement in the light absorption. On the other hand, we analyze the electron injection modelling two (mono and bidentate) adsorbing modes in WW3m@TiO2-WW8m@TiO2 using DFT (B3LYP+D3) calculations. Adsorption energies show that WW3m@TiO2-WW8m@TiO2 are coordinated in bidentate mode. In this sense, to analyze the density of states (DOS) we found that WW6m@TiO2 present the narrowest band gap (1.53 eV), promoting an easy electron injection, which could explain the origin of the highest overall efficiency of the solar cell for this porphyrin. Finally, dye regeneration, was studied through the free energy associated, ΔGregen, the values are between −6.61 and −6.93 eV for WW3m@TiO2-WW8m@TiO2 showing that this step is spontaneous and similar in all porphyrins.

KW - Computational studies

KW - N-annulated perylene Zn-porphyrin

KW - Solar cell

KW - TiO model

UR - http://www.scopus.com/inward/record.url?scp=84994048474&partnerID=8YFLogxK

U2 - 10.1016/j.commatsci.2016.09.042

DO - 10.1016/j.commatsci.2016.09.042

M3 - Article

VL - 126

SP - 514

EP - 527

JO - Computational Materials Science

JF - Computational Materials Science

SN - 0927-0256

ER -