Ground- and Excited-State Geometry Optimization of Small Organic Molecules with Quantum Monte Carlo

2013 ◽  
Vol 9 (12) ◽  
pp. 5513-5525 ◽  
Author(s):  
Riccardo Guareschi ◽  
Claudia Filippi
Keyword(s):  
Monte Carlo ◽  
Excited State ◽  
Quantum Monte Carlo ◽  
Organic Molecules ◽  
Geometry Optimization ◽  
Small Organic Molecules ◽  
Excited State Geometry Optimization

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>

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