Pyrrolidine-based dye-sensitized solar cells: A time-dependent density functional theory investigation of the excited state electronic properties

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Abstract

This work reports a theoretical study of the excited state properties of a series of original conjugated metal-free organic dyes containing the pyrrolidine (PYR) moiety. These compounds have recently been developed for dye-sensitized solar cells (DSSCs). Our polarizable continuum model time-dependent density functional theory-based procedure made it possible to efficiently and accurately evaluate (i) the vertical excitation energies, (ii) the related redox potentials, and (iii) the free enthalpies of injection. It turns out that the Becke-Half-and-Half-Lee-Yang-Parr functional, combined to the 6-311+G(2d,2p) basis set, gives reliable auxochromic shifts when the bulk solvation effects are included in the model. Indeed, the theoretical procedure provides excitation energies with a mean absolute deviation limited to ∼0.10 eV only. In addition, we give insights into the geometrical and electronic structures of the dyes, and we unravel the structural modifications that optimize the properties of PYR-based DSSCs. This investigation aims at improving the electron injection process, as well as the light harvesting efficiency (LHE) of the dyes. For this purpose, we considered a set of 17 new dyes, and starting from the basic five-block [PYR]-[phenyl]-[ethylene]-[thiophene]-[cyano acrylic acid] system (PYR-m′ structure), several modifications leading to better electron injection and comparable LHE properties have been proposed.
Original languageEnglish
Pages (from-to)2072-2084
Number of pages13
JournalInternational Journal of Quantum Chemistry
Volume112
Issue number9
DOIs
Publication statusPublished - 5 May 2012

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Excited states
Electronic properties
Density functional theory
Coloring Agents
solar cells
dyes
density functional theory
Electron injection
Excitation energy
electronics
excitation
injection
Thiophenes
Solvation
Electronic structure
Enthalpy
Metals
acrylic acid
thiophenes
solvation

Cite this

@article{650630555d844ad39b3f8b48517d88c4,
title = "Pyrrolidine-based dye-sensitized solar cells: A time-dependent density functional theory investigation of the excited state electronic properties",
abstract = "This work reports a theoretical study of the excited state properties of a series of original conjugated metal-free organic dyes containing the pyrrolidine (PYR) moiety. These compounds have recently been developed for dye-sensitized solar cells (DSSCs). Our polarizable continuum model time-dependent density functional theory-based procedure made it possible to efficiently and accurately evaluate (i) the vertical excitation energies, (ii) the related redox potentials, and (iii) the free enthalpies of injection. It turns out that the Becke-Half-and-Half-Lee-Yang-Parr functional, combined to the 6-311+G(2d,2p) basis set, gives reliable auxochromic shifts when the bulk solvation effects are included in the model. Indeed, the theoretical procedure provides excitation energies with a mean absolute deviation limited to ∼0.10 eV only. In addition, we give insights into the geometrical and electronic structures of the dyes, and we unravel the structural modifications that optimize the properties of PYR-based DSSCs. This investigation aims at improving the electron injection process, as well as the light harvesting efficiency (LHE) of the dyes. For this purpose, we considered a set of 17 new dyes, and starting from the basic five-block [PYR]-[phenyl]-[ethylene]-[thiophene]-[cyano acrylic acid] system (PYR-m′ structure), several modifications leading to better electron injection and comparable LHE properties have been proposed.",
author = "J. Preat and C. Michaux and E.A. Perp{\`e}te and J.-M. Andr{\'e}",
note = "Copyright 2012 Elsevier B.V., All rights reserved.",
year = "2012",
month = "5",
day = "5",
doi = "10.1002/qua.23153",
language = "English",
volume = "112",
pages = "2072--2084",
journal = "International Journal of Quantum Chemistry",
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T1 - Pyrrolidine-based dye-sensitized solar cells

T2 - A time-dependent density functional theory investigation of the excited state electronic properties

AU - Preat, J.

AU - Michaux, C.

AU - Perpète, E.A.

AU - André, J.-M.

N1 - Copyright 2012 Elsevier B.V., All rights reserved.

PY - 2012/5/5

Y1 - 2012/5/5

N2 - This work reports a theoretical study of the excited state properties of a series of original conjugated metal-free organic dyes containing the pyrrolidine (PYR) moiety. These compounds have recently been developed for dye-sensitized solar cells (DSSCs). Our polarizable continuum model time-dependent density functional theory-based procedure made it possible to efficiently and accurately evaluate (i) the vertical excitation energies, (ii) the related redox potentials, and (iii) the free enthalpies of injection. It turns out that the Becke-Half-and-Half-Lee-Yang-Parr functional, combined to the 6-311+G(2d,2p) basis set, gives reliable auxochromic shifts when the bulk solvation effects are included in the model. Indeed, the theoretical procedure provides excitation energies with a mean absolute deviation limited to ∼0.10 eV only. In addition, we give insights into the geometrical and electronic structures of the dyes, and we unravel the structural modifications that optimize the properties of PYR-based DSSCs. This investigation aims at improving the electron injection process, as well as the light harvesting efficiency (LHE) of the dyes. For this purpose, we considered a set of 17 new dyes, and starting from the basic five-block [PYR]-[phenyl]-[ethylene]-[thiophene]-[cyano acrylic acid] system (PYR-m′ structure), several modifications leading to better electron injection and comparable LHE properties have been proposed.

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