scholarly journals Charge-transfer excited states in the donor/acceptor interface from large-scale GW calculations

2019 ◽  
Vol 151 (11) ◽  
pp. 114109 ◽  
Author(s):  
Takatoshi Fujita ◽  
Yoshifumi Noguchi ◽  
Takeo Hoshi
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Large Scale ◽  
Donor Acceptor

scholarly journals Rational Design of TADF Polymers Using a Donor-Acceptor Monomer with Enhanced TADF Efficiency Induced by the Energy Alignment of Charge Transfer and Local Triplet Excited States

2016 ◽  
Vol 4 (4) ◽  
pp. 597-607 ◽  
Author(s):  
Roberto S. Nobuyasu ◽  
Zhongjie Ren ◽  
Gareth C. Griffiths ◽  
Andrei S. Batsanov ◽  
Przemyslaw Data ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Rational Design ◽  
Donor Acceptor ◽  
Triplet Excited States

scholarly journals Rational Design of TADF Polymers Using a Donor–Acceptor Monomer with Enhanced TADF Efficiency Induced by the Energy Alignment of Charge Transfer and Local Triplet Excited States

2016 ◽  
Vol 4 (5) ◽  
pp. 653-653 ◽  
Author(s):  
Roberto S. Nobuyasu ◽  
Zhongjie Ren ◽  
Gareth C. Griffiths ◽  
Andrei S. Batsanov ◽  
Przemyslaw Data ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Rational Design ◽  
Donor Acceptor ◽  
Triplet Excited States

Wechselwirkungen in Kristallen, 88 [1 - 3] Donator/Akzeptor - Komplexe von Alkylbenzolen, Pyren oder Perylen mit Tetrahalogen-p-benzochinonen: Strukturen und Eigenschaften / Interactions in Crystals, 88 [1 -3] Donor/Acceptor Complexes of Alkylbenzenes, Pyrene or Perylene and Tetrahalogen-p-benzoquinones: Structures and Properties

1996 ◽  
Vol 51 (11) ◽  
pp. 1521-1537 ◽  
Author(s):  
Hans Bock ◽  
Mark Sievert ◽  
Holger Schödel ◽  
Markus Kleine
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Complex Formation ◽  
Excited States ◽  
Structure Data ◽  
Structural Changes ◽  
Crystal Structure Data ◽  
Reduction Potentials ◽  
Structures And Properties ◽  
Donor Acceptor

The following mixed-stack donor/acceptor complexes {D · · · A }∞ have been crystallized and their structures determined: { 1 ,2,4,5-tetramethylbenzene · · · tetrabromo-p -benzoquinone}∞ , {hexamethylbenzene · · · tetrabromo-p-benzoquinone}∞ , { ( 1 ,2 ,4,5-tetramethyl-benzene)2 · · · tetrachloro -p -benzoquinone}∞ , {pyrene · · · tetrafluoro-p-benzoquinone}∞ , {pyrene · · · tetrabromo-p-benzoquinone}∞ and {perylene · · · tetrabromo-p-benzoquinone}∞ . They exhibit an interesting lattice packing, especially the 2:1 tripeldecker sandwich of tetrachloro-p-benzoquinone, which crystallizes in a herringbone pattern. Their interplanar distances are around 340 pm, i. e. two van der Waals π radii. None of them , however, exhibits in neither the donor nor the acceptor components significant structural changes due to complex formation. Their colours range from orange-red to black in the crystal and to green in H2CCl2 solution. Their long-wavelengths charge transfer absorption maxim a correspond to a lowering in excitation energy of up to 2 eV relative to that of the components. The different charge transfer in the ground and excited states of the donor/acceptor complexes investigated is further discussed referring to data such as cyclovoltammetric reduction potentials as w ell as to results from semiempirical calculations based on the crystal structure data determined and including configuration interaction.

Transitioning from Intraligand π,π* to Charge-Transfer Excited States Using Thiophene-Based Donor–Acceptor Systems

2020 ◽  
Vol 60 (1) ◽  
pp. 130-139
Author(s):  
James R. W. McLay ◽  
Joshua J. Sutton ◽  
Georgina E. Shillito ◽  
Christopher B. Larsen ◽  
Gregory S. Huff ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Donor Acceptor

scholarly journals Predicting Excitation Energies of Twisted Intramolecular Charge-Transfer States with Time-Dependent Density Functional Theory: Comparison with Experimental Measurements in the Gas-Phase and Solvents Ranging from Hexanes to Acetonitrile

2020 ◽  
Author(s):  
James Shee ◽  
Martin Head-Gordon
Keyword(s):  
Charge Transfer ◽  
Gas Phase ◽  
Excited States ◽  
Linear Response ◽  
Density Functional ◽  
Intramolecular Charge Transfer ◽  
Experimental Measurements ◽  
Excitation Energies ◽  
Donor And Acceptor ◽  
Donor Acceptor

Electronically-excited states characterized by intramolecular charge-transfer play an essential role in many biological processes and optical devices. The ability to make quantitative ab initio predictions of the relative energetics involved is a challenging yet desirable goal, especially for large molecules in solution. In this work we present a data set of 61 experimental measurements of absorption and emission processes, both in the gas phase and solvents representing a broad range of polarities, which involve intramolecular charge-transfer mediated by a non-zero, “twisted” dihedral angle between one or more donor and acceptor subunits. Among a variety of density functionals investigated within the framework of linear-response theory, the “optimally tuned” LRC-ωPBE functional, which utilizes a system-specific yet non-empirical procedure to specify the range-separation parameter, emerges as the preferred choice. For the entire set of excitation energies, involving changes in dipole moment ranging from 4 to >20 Debye, the mean signed and absolute errors are 0.02 and 0.18 eV, respectively (compared, e.g., to -0.30 and 0.30 for PBE0, 0.44 and 0.47 for LRC-ωPBEh, 0.83 and 0.83 for ωB97X-V). The performance of polarizable continuum solvation models for these charge-transfer excited states is closely examined, and clear trends emerge when measurements corresponding to the four small DMABN-like molecules and a charged species are excluded. We make the case that the large errors found only for small molecules in the gas phase and weak solvents cannot be expected to improve via the optimal tuning procedure, which enforces a condition that is exact only in the wellseparated donor-acceptor limit, and present empirical evidence implicating the outsized importance for small donor-acceptor systems of relaxation effects that cannot be accounted for by linear-response TDDFT within the adiabatic approximation. Finally, we demonstrate the utility of the optimally tuned density functional approach by targeting the charge-transfer states of a large biomimetic model system for light-harvesting structures in Photosystem II.

Wechselwirkungen in Kristallen, 89 [1 - 3] Donator/Akzeptor-Komplexe von Alkyl- und Aminobenzolen, Anthracen oder Pyren mit 1,3,5-Cyan-/Nitro-benzolen: Kristallisation, Strukturen und Elektronenspektren / Interactions in Crystals, 89 [ 1 - 3] Donor/Acceptor Complexes of Alkyl and Aminobenzenes, Anthracene or Pyrene and 1,3,5-Cyano/nitro-benzenes: Crystallisation, Structures and Electronic Spectra

1996 ◽  
Vol 51 (11) ◽  
pp. 1538-1554 ◽  
Author(s):  
Hans Bock ◽  
Klaus Ziemer ◽  
Christian Näther ◽  
Holger Schödel ◽  
Markus Kleine ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Complex Formation ◽  
Excited States ◽  
Structural Changes ◽  
Crystal Structure Data ◽  
Van Der Waals ◽  
Van Der Waals Interactions ◽  
Long Wavelength ◽  
Donor Acceptor

The following mixed-stack donor/acceptor complexes {D···A}∞ have been crystallized and their structures determined: {hexamethylbenzene···3,5-dicyano-1-nitrobenzene hexamethylbenzene···3,5-dinitro-1-cyanobenzene}∞, {pyrene···3,5-dinitro-1-cyanobenzene}∞, {anthracene···(3,5-dinitro-1-cyanobenzene)2}∞, {N,N-dimethylanilin···3,5-dinitro- 1-cyanobenzene}∞ and { 1-3-phenylenediamine···3,5-dinitro-1-cyanobenzene}∞. Their lattice packing consists of parallel layers, which contain either donors and acceptors as for hexamethylbenzene and pyrene or composite ones as in the 1:2 complex of anthracene with each one of the acceptors above and below its peripheral rings. The isostructural hexamethylbenzene complexes exhibit almost identical packing coefficients as well as a hexagonal coplanar arrangement of the C6(CH3)6 donors. Weak intermolecular van der Waals interactions are also observed between antiparallel cyano substituents. The interplanar n distances range between 334 and 353 pm, i. e. around 340 pm of two van der Waals n radii. In none of the complexes, however, significant structural changes in either the donor or the acceptor components due to the complex formation are observed. In both the crystals as well as in solution, the donor/acceptor complexes exhibit colours between yellow and red; their long-wavelength charge transfer absorption maxima, therefore, correspond to a lowering in excitation energy of only up to 1 eV relative to that of the components. The different charge transfer in the ground and the CT excited states is also discussed referring to other data such as vertical first ionization energies or interplanar distances {D···A}, as well as to results from semiempirical calculations based on the crystal structure data determined and including approximate configuration interaction.

Contrasting Behaviour of Exciplex Ensembles in the Diastereodifferentiating Paternò–Büchi Reaction of Chiral Cyanobenzoate with Naphthyl- and Phenylethenes on Direct or Charge-Transfer Excitation

2015 ◽  
Vol 68 (11) ◽  
pp. 1693 ◽  
Author(s):  
Keisuke Nagasaki ◽  
Yoshihisa Inoue ◽  
Tadashi Mori
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Charge Transfer Complex ◽  
Small Temperature ◽  
Acceptor Interaction ◽  
Subtle Change ◽  
Excited Species ◽  
Donor Acceptor ◽  
Charge Transfer Excitation ◽  
The Difference

The diastereodifferentiating Paternò–Büchi reaction of chiral cyanobenzoate with 1-(1-naphthyl)-1-phenylethene was compared with those with 1,1-diphenylethene on direct and charge-transfer excitations. By desymmetrization of the donor, four diastereomeric oxetane products were formed on photolysis in excellent combined yields. Increase in donor strength induced a stronger charge-transfer interaction both in ground and excited states. Thus, the difference in diastereoselectivities with two different excitation modes (i.e. direct versus charge-transfer) became less significant with a naphthyl derivative as donor. A subtle change of donor–acceptor interaction was shown to have profound effect on the nature of the excited-state complexes and thus the product (stereo)selectivities. Despite a small temperature dependence, an Eyring-type study on the diastereoselectivities confirmed that the excited charge-transfer complex is an excited species distinct from the conventional exciplex.

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