Excited states of polyene radical cations: limitations of Koopmans' theorem

1984 ◽  
Vol 106 (14) ◽  
pp. 3927-3933 ◽  
Author(s):  
Thomas Bally ◽  
Stephan Nitsche ◽  
Kuno Roth ◽  
Edwin Haselbach
Keyword(s):  
Excited States ◽  
Radical Cations ◽  
Koopmans Theorem

Isomerization Behavior of Halostilbene Radical Cations in the Excited States. Two-Color Photochemistry of Stilbene Derivatives

1994 ◽  
Vol 23 (8) ◽  
pp. 1371-1374 ◽  
Author(s):  
Yasunao Kuriyama ◽  
Fumiko Hashimoto ◽  
Masahiro Tsuchiya ◽  
Hirochika Sakuragi ◽  
Katsumi Tokumaru
Keyword(s):  
Excited States ◽  
Radical Cations ◽  
Stilbene Derivatives

Excited states in polyene radical cations. An ab initio theoretical study

1995 ◽  
Vol 236 (1-2) ◽  
pp. 167-176 ◽  
Author(s):  
M.P. Fülscher ◽  
S. Matzinger ◽  
T. Bally
Keyword(s):  
Ab Initio ◽  
Excited States ◽  
Theoretical Study ◽  
Radical Cations

Predicted geometries of porphyrin excited states and radical cations and anions

1991 ◽  
Vol 95 (24) ◽  
pp. 9728-9736 ◽  
Author(s):  
Kristine Prendergast ◽  
Thomas G. Spiro
Keyword(s):  
Excited States ◽  
Radical Cations

scholarly journals Hole-Mediated PhotoRedox Catalysis: Tris(p-Substituted)biarylaminium Radical Cations as Tunable, Precomplexing and Potent Photooxidants

2020 ◽  
Author(s):  
Shangze Wu ◽  
Jonas Zurauskas ◽  
Michal Domanski ◽  
Patrick Hitzfeld ◽  
Valeria Butera ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Excited State ◽  
Excited States ◽  
Organic Molecules ◽  
Radical Cations ◽  
Single Electron Transfer ◽  
Photoredox Catalysis ◽  
Small Organic Molecules ◽  
Fundamental Limitations ◽  
Ion Species

<p>Electrochemically-mediated Photoredox Catalysis emerged as a powerful synthetic technique in recent years, overcoming fundamental limitations of electrochemistry and photoredox catalysis in the single electron transfer activation of small organic molecules. However, the mechanism of how photoexcited radical ion species with ultrashort (picosecond-order) lifetimes could ever undergo productive photochemistry has eluded synthetic chemists. We report tri(<i>para</i>-substituted)biarylamines as a tunable class of electroactivated photocatalysts that become superoxidants in their photoexcited states, even able to oxidize molecules (such as dichlorobenzene and trifluorotoluene) beyond the solvent window limits of cyclic voltammetry. Furthermore, we demonstrate that precomplexation not only permits the excited state photochemistry of tris(<i>para</i>-substituted)biarylaminium cations, but enables and rationalizes the surprising photochemistry of their <i>higher-order</i> doublet (D<i><sub>n</sub></i>) excited states.</p>

Prediction of the photoelectron spectrum for XPY2 (X = H, F, Cl; Y = O, S) type of molecules by ab initio and DFT methods

2006 ◽  
Vol 84 (1) ◽  
pp. 5-9 ◽  
Author(s):  
Didier Bégué ◽  
Jean-marc Sotiropoulos ◽  
Claude Pouchan ◽  
Daisy Y Zhang
Keyword(s):  
Ab Initio ◽  
Density Functional ◽  
Radical Cations ◽  
Dft Methods ◽  
Functional Theory ◽  
Hartree Fock ◽  
Orbital Energies ◽  
Koopmans Theorem ◽  
Vertical Ionization Potentials ◽  
Hybrid Density Functional

The present study reports the theoretical vertical ionization potentials (IPs) for all the valence electrons in six XPY2 molecules by utilizing the corrected orbital energies calculated with three theoretical methods, namely, the ab initio Hartree–Fock (HF), and both the pure and hybrid density functional theory (DFT) methods at, respectively, the BLYP/6-311+G* and B3lYP/6-311+G* levels of theory. Evaluation of the numerical corrections to the orbital energies was achieved by comparisons with the IP values obtained via explicit computation of the energy differences between the neutral molecules and the corresponding radical cations (the ΔSCF method) and shows values from –0.9 to –1.9 eV for the HF, and positive values from 2.9 to 3.9 eV and from 1.8 to 2.4 eV for the pure and hybrid DFT methods, respectively. In contrast to the orbital energies, the ΔSCF method is shown to give consistent values among the three methods, as well as reasonable agreement with the experimental IP values.Key words: ionization potential, phosphorane, Koopmans' theorem, Janak's theorem.

Nature of the lowest excited states of neutral polyenyl radicals and polyene radical cations

2009 ◽  
Vol 131 (14) ◽  
pp. 144311 ◽  
Author(s):  
Jan Hendrik Starcke ◽  
Michael Wormit ◽  
Andreas Dreuw
Keyword(s):  
Excited States ◽  
Radical Cations

scholarly journals Calculations of the Optical Spectra of Hydrocarbon Radical Cations Based on Koopmans' Theorem

2007 ◽  
Vol 111 (9) ◽  
pp. 1667-1676 ◽  
Author(s):  
Stephen F. Nelsen ◽  
Michael N. Weaver ◽  
Daisuke Yamazaki ◽  
Koichi Komatsu ◽  
Rajendra Rathore ◽  
...  
Keyword(s):  
Radical Cations ◽  
Optical Spectra ◽  
Hydrocarbon Radical ◽  
Koopmans Theorem
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