Optical charge transfer transitions in supramolecular fullerene and porphyrin compounds

Краснов, Павел О.; Кузубов, А. А.; Kholtobina, Anastasia S.; Kovaleva, Evgenia A.; Kuzubova, M. V.

doi:10.1134/s0022476616040028

Cited by 2 publications

(2 citation statements)

References 47 publications

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“…The calculations were performed using GGA-PBE [45] functional on predetermined crystal structures of FeTPPCl and FeTPPOH•H2O from the Cambridge Crystallographic Data Centre (CCDC) database. Krasnov et al [51] performed a PDFT study of porphyrin:fullerene supramolecular compounds using models constructed from x-ray crystal structures determined by Boyd et al [52]. The PBE functional [45] with Grimme DFT-D2 [53] dispersion interaction correction was used to optimize the models of porphyrin:fullerene compounds.…”

Section: Porphyrin Nanostructures Using Crystal Geometriesmentioning

confidence: 99%

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

2020

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Porphyrins are fascinating molecules with applications spanning various scientific fields. In this review we present the use of periodic density functional theory (PDFT) calculations to study the structure, electronic properties, and reactivity of porphyrins on ordered two dimensional surfaces and in the formation of nanostructures. The focus of the review is to describe the application of PDFT calculations for bridging the gaps in experimental studies on porphyrin nanostructures and self-assembly on 2D surfaces. A survey of different DFT functionals used to study the porphyrin-based system as well as their advantages and disadvantages in studying these systems is presented.

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Section: Porphyrin Nanostructures Using Crystal Geometriesmentioning

confidence: 99%

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

2020

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“…Density functional theory (DFT) has been used extensively in the study of molecular and crystalline porphyrin systems. − DFT has also been used to study porphyrins and other large conjugated systems on surfaces. − True polymorphism has also been the subject of study by DFT methods. ,− Much less studied by DFT are systems with two components (tectons) making up the self-assembled monolayer. Examples include the porphyrin–coronene system, guest–host systems like the PBM2-coronene system, and the incorporation of Zn and Ag nitrates into pores created by trimesic acid cycles on graphite .…”

Section: Introductionmentioning

confidence: 99%

Computational Study of Solvent Incorporation into a Porphyrin Monolayer

Hipps,

Mazur

2024

J. Phys. Chem. C

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The density functional theory (DFT) is used to investigate the conversion from a solvent incorporated pseudopolymorph into a single-component monolayer. Calculations of thermodynamic properties for the surfaces in contact both with the gas phase and with the solvent are reported. In the case of wetted surfaces, a simple bond-additivity model, first proposed by Campbell and modified here, is used to augment the DFT calculations. The model predicts a dramatic reduction in desorption energies in the solvent as compared to the gas phase. Eyring's reaction rate theory is used to predict limiting desorption rates for guest (solvent) molecules from the pockets in the pseudopolymorph and for cobalt octaethylporphyrin (COEP) molecules in all structures. The pseudopolymorph studied here is a nearly rectangular lattice (REC) composed of two CoOEP and two molecules of either 1,2,4-trichlorobenzene (TCB) or toluene (TOL) supported on 63 atoms of Au(111). At sufficiently high initial concentrations of CoOEP, only a hexagonal unit cell (HEX) with two molecules of CoOEP, supported on 50 atoms of gold, is observed. Experimentally, the TCB-REC structure is more stable than the TOL-REC structure existing in the solution at initial mM concentrations of CoOEP in TCB as opposed to the initial μM concentration of CoOEP in toluene. Calculations here show that the HEX structure is the thermodynamically stable structure at all practical concentrations of CoOEP. Once the REC structure forms kinetically at low concentrations because of the vast excess of solvent on the surface, it is difficult to convert it to the more stable HEX structure. The difference in stability is primarily due to the difference in electronic adsorption energy of the solvents (TOL or TCB) and to the very low desorption rate of CoOEP. The adsorption energy of TCB has two important contributors: the adsorption energy onto Au alone and the intermolecular interactions between TCB and the CoOEP host lattice. Neither factor can be neglected. We also find that the planar adsorption of both TOL and TCB on Au(111) is the energetically preferred orientation when space is available on the surface. Rates of desorption are very sensitive to the solvent free activation energy and to the thermodynamic parameters required to convert the solvent free activation energy to one for the solvated surface. Small changes in the computed energy (of the order of 5%) can lead to a 1 order of magnitude change in rates. Further, the solvation model used does not provide the barrier to adsorption in the solution needed to determine values for the desorption activation energy in solution. Thus, the rates computed here for desorption into the solvent are limiting values.

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Optical charge transfer transitions in supramolecular fullerene and porphyrin compounds

Cited by 2 publications

References 47 publications

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

Computational Study of Solvent Incorporation into a Porphyrin Monolayer

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