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Title: A DFT analysis of the ground and charge-transfer excited states of Sc3N@Ih–C80 fullerene coupled with metal-free and zinc-phthalocyanine

Abstract

Endohedral metallofullerenes and phthalocyanine derivatives are recognized as excellent active materials in organic photovoltaics (OPVs). The tri-metallic nitride endohedral C80 fullerenes have greater absorption coefficients in the visible region and electron-accepting abilities similar to C60, which can allow for higher efficiencies in OPV devices. Here, we have investigated the ground and charge transfer excited states of two co-facial donor–acceptor (D–A) molecular conjugates formed by the non-covalent coupling of trimetallic nitride endohedral fullerene (Sc3N@Ih–C80) with metal-free (H2Pc) and zinc-phthalocyanine (ZnPc) chromophores using DFT calculations. The charge transfer (CT) excitation energies are calculated using the perturbative delta-SCF method that enforces orthogonality between the ground and excited states. The binding energies calculated using the PBE and DFT-D3 methods indicate that the dispersion effects play an important role in the stabilization of these complexes. The ground state dipole moment of the Sc3N@C80–H2Pc dyad is much larger than that of Sc3N@C80–ZnPc, but this is reversed in the excited state where the dipole moment of Sc3N@C80–ZnPc increases significantly. The lowest few excitation energies in the gas phase for the two complexes are very close, in the range of 1.51–2.66 eV for Sc3N@C80–ZnPc and 1.51–2.71 eV for the Sc3N@C80–H2Pc complex. However, the lower ionization potential and lowermore » exciton binding energy make the Sc3N@C80–ZnPc dyad a better candidate for OPVs as compared to the Sc3N@C80–H2Pc dyad.« less

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1]
  1. Univ. of Texas at El Paso, TX (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (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:
1544211
Alternate Identifier(s):
OSTI ID: 1476368
Grant/Contract Number:  
SC0006818; SC0002168; TG-DMR090071; SC0006818 and DE-SC0002168
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 20; Journal Issue: 40; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Amerikheirabadi, Fatemeh, Diaz, Carlos, Mohan, Neetha, Zope, Rajendra R., and Baruah, Tunna. A DFT analysis of the ground and charge-transfer excited states of Sc3N@Ih–C80 fullerene coupled with metal-free and zinc-phthalocyanine. United States: N. p., 2018. Web. doi:10.1039/C8CP03849J.
Amerikheirabadi, Fatemeh, Diaz, Carlos, Mohan, Neetha, Zope, Rajendra R., & Baruah, Tunna. A DFT analysis of the ground and charge-transfer excited states of Sc3N@Ih–C80 fullerene coupled with metal-free and zinc-phthalocyanine. United States. https://doi.org/10.1039/C8CP03849J
Amerikheirabadi, Fatemeh, Diaz, Carlos, Mohan, Neetha, Zope, Rajendra R., and Baruah, Tunna. 2018. "A DFT analysis of the ground and charge-transfer excited states of Sc3N@Ih–C80 fullerene coupled with metal-free and zinc-phthalocyanine". United States. https://doi.org/10.1039/C8CP03849J. https://www.osti.gov/servlets/purl/1544211.
@article{osti_1544211,
title = {A DFT analysis of the ground and charge-transfer excited states of Sc3N@Ih–C80 fullerene coupled with metal-free and zinc-phthalocyanine},
author = {Amerikheirabadi, Fatemeh and Diaz, Carlos and Mohan, Neetha and Zope, Rajendra R. and Baruah, Tunna},
abstractNote = {Endohedral metallofullerenes and phthalocyanine derivatives are recognized as excellent active materials in organic photovoltaics (OPVs). The tri-metallic nitride endohedral C80 fullerenes have greater absorption coefficients in the visible region and electron-accepting abilities similar to C60, which can allow for higher efficiencies in OPV devices. Here, we have investigated the ground and charge transfer excited states of two co-facial donor–acceptor (D–A) molecular conjugates formed by the non-covalent coupling of trimetallic nitride endohedral fullerene (Sc3N@Ih–C80) with metal-free (H2Pc) and zinc-phthalocyanine (ZnPc) chromophores using DFT calculations. The charge transfer (CT) excitation energies are calculated using the perturbative delta-SCF method that enforces orthogonality between the ground and excited states. The binding energies calculated using the PBE and DFT-D3 methods indicate that the dispersion effects play an important role in the stabilization of these complexes. The ground state dipole moment of the Sc3N@C80–H2Pc dyad is much larger than that of Sc3N@C80–ZnPc, but this is reversed in the excited state where the dipole moment of Sc3N@C80–ZnPc increases significantly. The lowest few excitation energies in the gas phase for the two complexes are very close, in the range of 1.51–2.66 eV for Sc3N@C80–ZnPc and 1.51–2.71 eV for the Sc3N@C80–H2Pc complex. However, the lower ionization potential and lower exciton binding energy make the Sc3N@C80–ZnPc dyad a better candidate for OPVs as compared to the Sc3N@C80–H2Pc dyad.},
doi = {10.1039/C8CP03849J},
url = {https://www.osti.gov/biblio/1544211}, journal = {Physical Chemistry Chemical Physics. PCCP},
issn = {1463-9076},
number = 40,
volume = 20,
place = {United States},
year = {Fri Sep 14 00:00:00 EDT 2018},
month = {Fri Sep 14 00:00:00 EDT 2018}
}

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