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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

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/C8CP03849J· OSTI ID:1544211
 [1];  [1]; ORCiD logo [1];  [1];  [1]
  1. Univ. of Texas at El Paso, TX (United States)
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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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0006818; SC0002168; TG-DMR090071; SC0006818 and DE-SC0002168
OSTI ID:
1544211
Alternate ID(s):
OSTI ID: 1476368
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 40; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

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