Ground and excited states of zinc phthalocyanine, zinc tetrabenzoporphyrin, and azaporphyrin analogs using DFT and TDDFT with Franck-Condon analysis

Theisen, Rebekah F.; Huang, Liang; Fleetham, Tyler; Adams, James B.; Li, Jian

doi:10.1063/1.4913757

Cited by 37 publications

(42 citation statements)

References 67 publications

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“…Magnetic circular dichroism data indicate that this region contains both a vibronic side‐band of the Q transition and an additional electronic transition. However, recent computational results suggest that Q′ is well‐modelled exclusively as a vibronic side‐band of Q …”

Section: Resultssupporting

confidence: 91%

“…We have not identified any possible spin‐singlet excited states, symmetry‐forbidden or otherwise, in the correct energy region. Therefore, in agreement with Theisen et al, we can rule out the hypothesis that Q′ corresponds to a orbitally symmetry‐forbidden transition “borrowing” intensity from a symmetry‐allowed transition purely through vibronic coupling.…”

Section: Resultssupporting

confidence: 63%

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Coupled cluster calculations provide a one‐to‐one mapping between calculated and observed transition energies in the electronic absorption spectrum of zinc phthalocyanine

Wallace

Williamson

Crittenden

2017

Int J of Quantum Chemistry

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All transitions in the experimentally designated and numbered Q, B, and N bands (< 4.8 eV) of the electronic absorption spectrum of zinc phthalocyanine (ZnPc) are assigned on the basis of one‐to‐one agreement between calculated and experimentally observed transition energies and oscillator strengths. Each band in this range of the spectrum represents a ligand‐based transition that originates from a combination of occupied orbitals and terminates in the lowest unoccupied molecular orbital (LUMO, 6eg(π)). Transition energies in the L and C regions (4.8–6.5 eV) are harder to capture quantitatively, due to the partial Rydberg character of some of the excited states, and so are tentatively assigned here. Most transitions in this range correspond to excitations from the HOMO or lower‐energy orbitals to π orbitals above the LUMO.

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Section: Resultssupporting

confidence: 91%

Section: Resultssupporting

confidence: 63%

Coupled cluster calculations provide a one‐to‐one mapping between calculated and observed transition energies in the electronic absorption spectrum of zinc phthalocyanine

Wallace

Williamson

Crittenden

2017

Int J of Quantum Chemistry

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“…In the case of TiOPc, the energy gap (2.37 eV) was identified to be wavelength at 523 nm. In the case of ZnPc, The Eg (2.20 eV) was similar to literature data of ZnPc (2.19 eV) [9]. Electrostatic potential (ESP) of the phthalocyanines are shown in Fig.…”

Section: Resultssupporting

confidence: 63%

“…Zinc phthalocyanine derivatives (ZnPc) has been used as a good donor of semi conductive materials in organic solar cells, electronic application and devices [8]. The phthalocyanine derivatives had energy separation due to asymmetry of nitrogen atom allocation [9]. Several derivatives with chemical substituents of phenyl group had a molecular interaction, yielding an increase of the energy conversion efficiency.…”

Section: Introductionmentioning

confidence: 99%

Electronic structures and magnetic/optical properties of metal phthalocyanine complexes

Baba¹,

Suzuki²,

Oku³

2016

AIP Conference Proceedings

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Ground state electronic structures and spectra of zinc complexes of porphyrin, tetraazaporphyrin, tetrabenzoporphyrin, and phthalocyanine: A density functional theory study Abstract. Electronic structures and magnetic / optical properties of metal phthalocyanine complexes were studied by quantum calculations using density functional theory. Effects of central metal and expansion of π orbital on aromatic ring as conjugation system on the electronic structures, magnetic, optical properties and vibration modes of infrared and Raman spectra of metal phthalocyanines were investigated. Electron and charge density distribution and energy levels near frontier orbital and excited states were influenced by the deformed structures varied with central metal and charge. The magnetic parameters of chemical shifts in 13 C-nuclear magnetic resonance ( 13 C-NMR), principle g-tensor, A-tensor, V-tensor of electric field gradient and asymmetry parameters derived from the deformed structures with magnetic interaction of nuclear quadruple interaction based on electron and charge density distribution with a bias of charge near ligand under crystal field.

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“…These uncontentious assignments are unanimously supported in the literature. [18,53,28,64,65,66,67,68,69,70,71,72,73,74,75,76,18] For CuPc, inspection of Figure 2 suggests that an alternative configuration may be possible, with two electrons in the d z 2 orbital and only one in the ligand HOMO, which would correspond to a closed-shell metal cation surrounded by a radical anion ligand. However, this physically implausible state is higher in energy than the depicted configuration, both because the d x 2 −y 2 orbital is less stable than the ligand HOMO and because it is harder to pair electrons within the more compact metal-centred orbital.…”

Section: Nipc Cupc Znpcmentioning

confidence: 99%

CASSCF-based explicit ligand field models clarify the ground state electronic structures of transition metal phthalocyanines (MPc; M = Mn, Fe, Co, Ni, Cu, Zn)

2016

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Multireference electronic structure methods are used to assign ground state electronic configurations for a series of metallophthalocyanines. Ligand orbital occupancies remain constant across the period and are consistent with a formal 2– charge on the ligand. The d electron configurations of some metallophthalocyanines are straightforward and can be unambiguously assigned, (dxy)2(dxz,dyz)2,2( [Formula: see text])2([Formula: see text])n, with n = 2, 1, 0, respectively, for ZnPc, CuPc, and NiPc. Controversies over ground state electronic structure assignments for other metallophthalocyanines arise due to multiple complicating factors: accidental near-degeneracies, environmental effects, and different ligand field models used in interpreting experimental spectra. We demonstrate that explicit ligand field models provide more reliable and consistent interpretations of experimental data than implicit, parameterized alternatives. On this basis, we assign gas-phase electronic ground states for MnPc, (dxy)2(dxz,dyz)1,1([Formula: see text])1 and CoPc, (dxy)2(dxz,dyz)2,2([Formula: see text])1, and show that the ground state of FePc cannot be resolved to a single state, with two near-degenerate states that are likely spin-orbit coupled: (dxy)2(dxz,dyz)1,1( [Formula: see text])2 and (dxy)2(dxz,dyz)2,1([Formula: see text])1. Remaining differences between computational predictions and experimental observations are small and may be ascribed primarily to environmental effects but are also partly due to incomplete modelling of electron correlation.

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Ground and excited states of zinc phthalocyanine, zinc tetrabenzoporphyrin, and azaporphyrin analogs using DFT and TDDFT with Franck-Condon analysis

Cited by 37 publications

References 67 publications

Coupled cluster calculations provide a one‐to‐one mapping between calculated and observed transition energies in the electronic absorption spectrum of zinc phthalocyanine

Coupled cluster calculations provide a one‐to‐one mapping between calculated and observed transition energies in the electronic absorption spectrum of zinc phthalocyanine

Electronic structures and magnetic/optical properties of metal phthalocyanine complexes

CASSCF-based explicit ligand field models clarify the ground state electronic structures of transition metal phthalocyanines (MPc; M = Mn, Fe, Co, Ni, Cu, Zn)

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