Evaluation of charge-transfer rates in fullerene-based donor–acceptor dyads with different density functional approximations

Besalú-Sala, Pau; Voityuk, Alexander A.; Luis, Josep M.; Solà, Miquel

doi:10.1039/d0cp06510b

Cited by 18 publications

(18 citation statements)

References 73 publications

(76 reference statements)

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“…[21] Recently, some of us have benchmarked different density functional approximations and showed that CAM-B3LYP functional is the best choice for evaluation of charge-transfer rates in fullerene-based materials. [22] The empirical dispersion D3 correction was computed using the Becke-Johnson damping scheme. [23] The population analysis and calculation of Hirshfeld [24] and CM5 [25] charges were carried out with the Gaussian 16 program.…”

Section: Computational Detailsmentioning

confidence: 99%

The Hunter Falls Prey: Photoinduced Oxidation of C₆₀ in Inclusion Complex with Perfluorocycloparaphenylene

Stasyuk

Solà

et al. 2022

ChemPhysChem

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Perfluorocycloparaphenylenes (PFCPPs) are cycloparaphenylenes (CPPs) in which all hydrogen atoms have been replaced by fluorine atoms. Like CPPs, PFCPPs are highly strained, hoop‐shaped π‐conjugated molecules. In this article, we report a computational modeling of photoinduced electron transfer processes in the inclusion complex of PF[10]CPP with C60 fullerene. Its unique feature is the favorable electron transfer from C60 to the host molecule. The photooxidation of C60 is predicted to occur on a sub‐nanosecond timescale. The PF[10]CPP⊃C60 dyad is the first nanoring‐fullerene complex in which C60 acts as an electron donor in the photoinduced charge separation.

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Section: Computational Detailsmentioning

confidence: 99%

The Hunter Falls Prey: Photoinduced Oxidation of C₆₀ in Inclusion Complex with Perfluorocycloparaphenylene

Stasyuk

Solà

et al. 2022

ChemPhysChem

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“… 16 , 17 The CAMY-B3LYP functional has shown to provide accurate results for charge-transfer excitations in naphthalene derivatives and is therefore a suitable functional to study the PAHs in this work. 23 For more detailed information on the CAMY-B3LYP functional, we refer to ref ( 22b ).…”

Section: Computational Detailsmentioning

confidence: 99%

Polycyclic Aromatic Hydrocarbons (PAHs) in Interstellar Ices: A Computational Study into How the Ice Matrix Influences the Ionic State of PAH Photoproducts

Brinck

Nieuwland

Werf

et al. 2022

ACS Earth Space Chem.

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It has been experimentally observed that water–ice-embedded polycyclic aromatic hydrocarbons (PAHs) form radical cations when exposed to vacuum UV irradiation, whereas ammonia-embedded PAHs lead to the formation of radical anions. In this study, we explain this phenomenon by investigating the fundamental electronic differences between water and ammonia, the implications of these differences on the PAH–water and PAH–ammonia interaction, and the possible ionization pathways in these complexes using density functional theory (DFT) computations. In the framework of the Kohn–Sham molecular orbital (MO) theory, we show that the ionic state of the PAH photoproducts results from the degree of occupied–occupied MO mixing between the PAHs and the matrix molecules. When interacting with the PAH, the lone pair-type highest occupied molecular orbital (HOMO) of water has poor orbital overlap and is too low in energy to mix with the filled π-orbitals of the PAH. As the lone-pair HOMO of ammonia is significantly higher in energy and has better overlap with filled π-orbitals of the PAH, the subsequent Pauli repulsion leads to mixed MOs with both PAH and ammonia character. By time-dependent DFT calculations, we demonstrate that the formation of mixed PAH–ammonia MOs opens alternative charge-transfer excitation pathways as now electronic density from ammonia can be transferred to unoccupied PAH levels, yielding anionic PAHs. As this pathway is much less available for water-embedded PAHs, charge transfer mainly occurs from localized PAH MOs to mixed PAH–water virtual levels, leading to cationic PAHs.

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“…32,33 The empirical dispersion D3 correction was included using the Becke-Johnson damping scheme. 34,35 Vertical excitation energies were calculated using the TDA formalism 36 with the range-separated CAM-B3LYP 37,38 functional and the def2-SVP basis set, 32,33 as implemented in the Gaussian 16 (rev. A03) program.…”

Section: Methodsmentioning

confidence: 99%

Nitrogen-doped molecular bowls as electron donors in photoinduced electron transfer reactions

Stasyuk

Solà

et al. 2022

Nanoscale Adv.

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Evaluation of charge-transfer rates in fullerene-based donor–acceptor dyads with different density functional approximations

Abstract: The shift towards renewable energy is one of the main challenges of this generation. Dye-sensitized solar cells (DSSC), based on donor-acceptor architectures, can help on this transition as they present...

Cited by 18 publications

References 73 publications

The Hunter Falls Prey: Photoinduced Oxidation of C₆₀ in Inclusion Complex with Perfluorocycloparaphenylene

The Hunter Falls Prey: Photoinduced Oxidation of C₆₀ in Inclusion Complex with Perfluorocycloparaphenylene

Polycyclic Aromatic Hydrocarbons (PAHs) in Interstellar Ices: A Computational Study into How the Ice Matrix Influences the Ionic State of PAH Photoproducts

Nitrogen-doped molecular bowls as electron donors in photoinduced electron transfer reactions

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Evaluation of charge-transfer rates in fullerene-based donor–acceptor dyads with different density functional approximations

Abstract: The shift towards renewable energy is one of the main challenges of this generation. Dye-sensitized solar cells (DSSC), based on donor-acceptor architectures, can help on this transition as they present...

Cited by 18 publications

References 73 publications

The Hunter Falls Prey: Photoinduced Oxidation of C60 in Inclusion Complex with Perfluorocycloparaphenylene

The Hunter Falls Prey: Photoinduced Oxidation of C60 in Inclusion Complex with Perfluorocycloparaphenylene

Polycyclic Aromatic Hydrocarbons (PAHs) in Interstellar Ices: A Computational Study into How the Ice Matrix Influences the Ionic State of PAH Photoproducts

Nitrogen-doped molecular bowls as electron donors in photoinduced electron transfer reactions

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The Hunter Falls Prey: Photoinduced Oxidation of C₆₀ in Inclusion Complex with Perfluorocycloparaphenylene

The Hunter Falls Prey: Photoinduced Oxidation of C₆₀ in Inclusion Complex with Perfluorocycloparaphenylene