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Title: Excited States of Light-Harvesting Systems Based on Fullerene/Graphene Oxide and Porphyrin/Smaragdyrin

Abstract

In this work, we present a theoretical study at the density functional theory (DFT) level and time-dependent DFT of the ground and singlet excited states of electron donor–acceptor complexes formed by porphyrin (TPP)/smaragdyrin (TPOS) (expanded porphyrin), as light-harvesting systems, and fullerene (C 60)/graphene oxide (GO), as acceptor nanocarbon structure. We investigate the effect of the nanocarbon on UV–vis electronic absorption of porphyrin/smaragdyrin, using the functionals B3LYP, PBE, M06, and wB97XD. The results showed the lowest deviation of the Q-band for the functional M06 (0.01–0.02 eV). Electronic absorption spectra calculated for the complexes with M06 predict that (a) graphene oxide increases the intensity of the Soret band, (b) fullerene produces a red-shift of the Q bands (4 nm) with respect to graphene oxide, and (c) smaragdyrin causes a red-shift of Q (27–48 nm) and Soret (37 nm) absorption bands as compared to porphyrin. We also investigate the effect of the nanocarbon structure on the charge-transfer (CT) excited states. Using the perturbative delta-SCF method with the PBE functional, we found that the charge-transfer excitation energy increases as TPOS-C 60 (2.53 eV) < TPP-GO (2.89 eV) < TPP-C 60 (3.01 eV) < TPOS-GO (3.28 eV). The presence of a nanocarbon structure affects moremore » strongly smaragdyrin (~0.8 eV) than porphyrin (~0.1 eV). We show that the binding between smaragdyrin and fullerene C 60 favors the charge separation states with a lower energy cost, which means that these systems present an advantage for its application in photovoltaic cells.« less

Authors:
ORCiD logo [1];  [1];  [2];  [3]
  1. Univ. de Santiago de Chile (USACH), Santiago (Chile). Lab. de Química Teórica, Facultad de Química y Biología
  2. Univ. of Texas at El Paso, TX (United States). Dept. of Physics
  3. Univ. of Texas at El Paso, TX (United States). Dept. of Physics
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1480452
Grant/Contract Number:  
SC0002168
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 9; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Cárdenas-Jirón, Gloria, Borges-Martínez, Merlys, Sikorski, Ember, and Baruah, Tunna. Excited States of Light-Harvesting Systems Based on Fullerene/Graphene Oxide and Porphyrin/Smaragdyrin. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.6b12452.
Cárdenas-Jirón, Gloria, Borges-Martínez, Merlys, Sikorski, Ember, & Baruah, Tunna. Excited States of Light-Harvesting Systems Based on Fullerene/Graphene Oxide and Porphyrin/Smaragdyrin. United States. https://doi.org/10.1021/acs.jpcc.6b12452
Cárdenas-Jirón, Gloria, Borges-Martínez, Merlys, Sikorski, Ember, and Baruah, Tunna. Tue . "Excited States of Light-Harvesting Systems Based on Fullerene/Graphene Oxide and Porphyrin/Smaragdyrin". United States. https://doi.org/10.1021/acs.jpcc.6b12452. https://www.osti.gov/servlets/purl/1480452.
@article{osti_1480452,
title = {Excited States of Light-Harvesting Systems Based on Fullerene/Graphene Oxide and Porphyrin/Smaragdyrin},
author = {Cárdenas-Jirón, Gloria and Borges-Martínez, Merlys and Sikorski, Ember and Baruah, Tunna},
abstractNote = {In this work, we present a theoretical study at the density functional theory (DFT) level and time-dependent DFT of the ground and singlet excited states of electron donor–acceptor complexes formed by porphyrin (TPP)/smaragdyrin (TPOS) (expanded porphyrin), as light-harvesting systems, and fullerene (C60)/graphene oxide (GO), as acceptor nanocarbon structure. We investigate the effect of the nanocarbon on UV–vis electronic absorption of porphyrin/smaragdyrin, using the functionals B3LYP, PBE, M06, and wB97XD. The results showed the lowest deviation of the Q-band for the functional M06 (0.01–0.02 eV). Electronic absorption spectra calculated for the complexes with M06 predict that (a) graphene oxide increases the intensity of the Soret band, (b) fullerene produces a red-shift of the Q bands (4 nm) with respect to graphene oxide, and (c) smaragdyrin causes a red-shift of Q (27–48 nm) and Soret (37 nm) absorption bands as compared to porphyrin. We also investigate the effect of the nanocarbon structure on the charge-transfer (CT) excited states. Using the perturbative delta-SCF method with the PBE functional, we found that the charge-transfer excitation energy increases as TPOS-C60 (2.53 eV) < TPP-GO (2.89 eV) < TPP-C60 (3.01 eV) < TPOS-GO (3.28 eV). The presence of a nanocarbon structure affects more strongly smaragdyrin (~0.8 eV) than porphyrin (~0.1 eV). We show that the binding between smaragdyrin and fullerene C60 favors the charge separation states with a lower energy cost, which means that these systems present an advantage for its application in photovoltaic cells.},
doi = {10.1021/acs.jpcc.6b12452},
url = {https://www.osti.gov/biblio/1480452}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 9,
volume = 121,
place = {United States},
year = {2017},
month = {2}
}

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Synthesis of Novel Symmetric Porphyrin Schiff Base Dimers by Solid–Liquid Reaction Methodology
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Quantum chemical studies of porphyrin‐ and expanded porphyrin‐based systems and their potential applications in nanoscience. Latin America research review
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