Valence-band electronic structure of iron phthalocyanine: An experimental and theoretical photoelectron spectroscopy study

Brena, Barbara; Puglia, Carla; Simone, Monica de; Coreno, Marcello; Tarafder, Kartick; Feyer, Vitaliy; Banerjee, Rabin; Göthelid, Emmanuelle; Sanyal, Biplab; Oppeneer, Peter M.; Eriksson, Olle

doi:10.1063/1.3554212

Cited by 56 publications

(60 citation statements)

References 30 publications

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“…This agreement shows that a (range-separated or conventional) hybrid can be highly effective in the quantitative mitigation of SIEs, even though it is not rigorously self-interaction free because only a fraction of exact exchange is employed in the short range. Indeed, similar observations have been made for many other molecular systems, 33−35,39,53,58,61,112,116 often by comparison to experimental results, but also by comparison to SIC. 36,68 This rules out that the poor description of the “ring-shaped” (orange-colored) π orbital by OT-RSH is due to a general lack of balance in the description of π and σ orbitals owing to the SIE.…”

Section: Prototypical Aromatic Rings—results and Discussionsupporting

confidence: 77%

Outer-valence Electron Spectra of Prototypical Aromatic Heterocycles from an Optimally Tuned Range-Separated Hybrid Functional

Egger

Weissman

Refaely-Abramson

et al. 2014

J. Chem. Theory Comput.

136

180

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Density functional theory with optimally tuned range-separated hybrid (OT-RSH) functionals has been recently suggested [Refaely-Abramson et al. Phys. Rev. Lett.2012, 109, 226405] as a nonempirical approach to predict the outer-valence electronic structure of molecules with the same accuracy as many-body perturbation theory. Here, we provide a quantitative evaluation of the OT-RSH approach by examining its performance in predicting the outer-valence electron spectra of several prototypical gas-phase molecules, from aromatic rings (benzene, pyridine, and pyrimidine) to more complex organic systems (terpyrimidinethiol and copper phthalocyanine). For a range up to several electronvolts away from the frontier orbital energies, we find that the outer-valence electronic structure obtained from the OT-RSH method agrees very well (typically within ∼0.1–0.2 eV) with both experimental photoemission and theoretical many-body perturbation theory data in the GW approximation. In particular, we find that with new strategies for an optimal choice of the short-range fraction of Fock exchange, the OT-RSH approach offers a balanced description of localized and delocalized states. We discuss in detail the sole exception found—a high-symmetry orbital, particular to small aromatic rings, which is relatively deep inside the valence state manifold. Overall, the OT-RSH method is an accurate DFT-based method for outer-valence electronic structure prediction for such systems and is of essentially the same level of accuracy as contemporary GW approaches, at a reduced computational cost.

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Section: Prototypical Aromatic Rings—results and Discussionsupporting

confidence: 77%

Outer-valence Electron Spectra of Prototypical Aromatic Heterocycles from an Optimally Tuned Range-Separated Hybrid Functional

Egger

Weissman

Refaely-Abramson

et al. 2014

J. Chem. Theory Comput.

136

180

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“…Photoelectron spectroscopy of FePc in gas phase 30 can be the nearest case for this purpose. Another earlier spectroscopy was reported 31 for the molecule in solvent, concluding A 2 g as its ground state configuration because only this configuration can explain the observed shape of spectrum.…”

Section: Discussionmentioning

confidence: 99%

New Insight into the Ground State of FePc: A Diffusion Monte Carlo Study

Ichibha

Hou

Hongo

2017

Sci Rep

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We have applied DMC to evaluate relative stability of the possible electronic configurations of an isolated FePc under D 4h symmetry, considering some fixed nodes generated from different methods. They predict A 2g ground state consistently, supporting preceding DFT studies, with confidence overcoming the ambiguity about exchange-correlation (XC) functionals. By comparing DMC with several XC, we clarified the importance of the short-range exchange to describe the relative stability. We examined why the predicted A 2g is excluded from possible ground states in the recent ligand field based model. Simplified assumptions made in the superposition model are identified to give unreasonably less energy gain for A 2g when compared with the reality. The state is found to have possible reasons for the stabilization, reducing the occupations from an unstable anti-bonding orbital, avoiding double occupation of a spatially localized orbital, and gaining exchange energy by putting a triplet spin pair in degenerate orbitals.

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“…This phenomena is also observed for other metallophthalocyanines (particularly for NiPc; for some other metallic cations, HOMO-1 correspond to 3d-like orbitals). 29,30 For naphthalocyanines, N-meso atoms participate in HOMO-1, but its contribution is small.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Photophysical and Photochemical Properties and Aggregation Behavior of Phthalocyanine and Naphthalocyanine Derivatives

Souza¹,

Antonio²,

Zanotto³

et al. 2017

J. Braz. Chem. Soc.

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The photophysical and photochemical properties of phthalocyanine and naphthalocyanine with similar structures were studied in solution and with density-functional theory (DFT) computational method. The extended π-conjugated system in naphthalocyanines causes a bathochromic shift in UV-Vis, emission and excitation bands, and promotes lesser generation of singlet oxygen in solution when compared to phthalocyanines. Time dependent DFT (TD-DFT) calculations point out the molecular orbitals involved in Q-band transition, corresponding to highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) transition with a concentration of charge along x-axis, while the transition to LUMO+1 is in y-axis direction. The presence of tert-butyl substituents does not affect the molecular orbitals shape, but affect their energies. Aggregation studies in dimethyl sulfoxide (DMSO):water solutions showed that naphthalocyanines studied have more aggregation tendency than the phthalocyanines. DFT studies indicated that stacked-dimers are preferred to rotated-stacked conformation due the interaction between Zn II and nitrogen atom from different monomers.

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Valence-band electronic structure of iron phthalocyanine: An experimental and theoretical photoelectron spectroscopy study

Cited by 56 publications

References 30 publications

Outer-valence Electron Spectra of Prototypical Aromatic Heterocycles from an Optimally Tuned Range-Separated Hybrid Functional

Outer-valence Electron Spectra of Prototypical Aromatic Heterocycles from an Optimally Tuned Range-Separated Hybrid Functional

New Insight into the Ground State of FePc: A Diffusion Monte Carlo Study

Photophysical and Photochemical Properties and Aggregation Behavior of Phthalocyanine and Naphthalocyanine Derivatives

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