Stripping dynamics in the reactions of electronically excited carbon atoms, C(1D), with ethylene and propylene—production of propargyl and methylpropargyl radicals

2002 ◽  
Vol 116 (4) ◽  
pp. 1318-1324 ◽  
Author(s):  
R. I. Kaiser ◽  
T. L. Nguyen ◽  
A. M. Mebel ◽  
Y. T. Lee
Keyword(s):  
Electronically Excited ◽  
Propylene Production

Carbon-Heteroatom Cross-Coupling via an Electronically Excited Nickel (II) Complex

2019 ◽  
Author(s):  
Randolph Escobar ◽  
Jeffrey Johannes
Keyword(s):  
Energy Transfer ◽  
Functional Groups ◽  
Cross Coupling ◽  
Reductive Elimination ◽  
Aryl Halides ◽  
Coupling Reactions ◽  
General Methodology ◽  
Cross Coupling Reactions ◽  
Electronically Excited ◽  
Energy Transfer Pathway

<div>While carbon-heteroatom cross coupling reactions have been extensively studied, many methods are specific and</div><div>limited to a set of substrates or functional groups. Reported here is a method that allows for C-O, C-N and C-S cross coupling reactions under one general methodology. We propose that an energy transfer pathway, in which an iridium photosensitizer produces an excited nickel (II) complex, is responsible for the key reductive elimination step that couples aryl halides to 1° and 2° alcohols, anilines, thiophenols, carbamates and sulfonamides.</div>

Fluorescence Quenching of Aminodiphenylamines with Chloromethanes

2002 ◽  
Vol 67 (8) ◽  
pp. 1154-1164 ◽  
Author(s):  
Nachiappan Radha ◽  
Meenakshisundaram Swaminathan
Keyword(s):  
Charge Transfer ◽  
Fluorescence Quenching ◽  
Ground State ◽  
Rate Constants ◽  
Quenching Mechanism ◽  
Quenching Rate ◽  
Charge Transfer Interaction ◽  
Electronically Excited ◽  
A Charge

The fluorescence quenching of 2-aminodiphenylamine (2ADPA), 4-aminodiphenylamine (4ADPA) and 4,4'-diaminodiphenylamine (DADPA) with tetrachloromethane, chloroform and dichloromethane have been studied in hexane, dioxane, acetonitrile and methanol as solvents. The quenching rate constants for the process have also been obtained by measuring the lifetimes of the fluorophores. The quenching was found to be dynamic in all cases. For 2ADPA and 4ADPA, the quenching rate constants of CCl4 and CHCl3 depend on the viscosity, whereas in the case of CH2Cl2, kq depends on polarity. The quenching rate constants for DADPA with CCl4 are viscosity-dependent but the quenching with CHCl3 and CH2Cl2 depends on the polarity of the solvents. From the results, the quenching mechanism is explained by the formation of a non-emissive complex involving a charge-transfer interaction between the electronically excited fluorophores and ground-state chloromethanes.

scholarly journals Full-dimensional quantum stereodynamics of the non-adiabatic quenching of OH(A2Σ+) by H2

2021 ◽  
Author(s):  
Bin Zhao ◽  
Shanyu Han ◽  
Christopher L. Malbon ◽  
Uwe Manthe ◽  
David. R. Yarkony ◽  
...  
Keyword(s):  
Quantum Dynamics ◽  
Previous Analysis ◽  
Branching Ratio ◽  
Energy Matrix ◽  
Elastic Channel ◽  
Electronically Excited ◽  
Oppenheimer Approximation ◽  
Electronic Motion ◽  
Adiabatic Dynamics ◽  
Good Agreement

AbstractThe Born–Oppenheimer approximation, assuming separable nuclear and electronic motion, is widely adopted for characterizing chemical reactions in a single electronic state. However, the breakdown of the Born–Oppenheimer approximation is omnipresent in chemistry, and a detailed understanding of the non-adiabatic dynamics is still incomplete. Here we investigate the non-adiabatic quenching of electronically excited OH(A2Σ+) molecules by H2 molecules using full-dimensional quantum dynamics calculations for zero total nuclear angular momentum using a high-quality diabatic-potential-energy matrix. Good agreement with experimental observations is found for the OH(X2Π) ro-vibrational distribution, and the non-adiabatic dynamics are shown to be controlled by stereodynamics, namely the relative orientation of the two reactants. The uncovering of a major (in)elastic channel, neglected in a previous analysis but confirmed by a recent experiment, resolves a long-standing experiment–theory disagreement concerning the branching ratio of the two electronic quenching channels.

High-Fidelity First Principles Nonadiabaticity: Diabatization, Analytic Representation of Global Diabatic Potential Energy Matrices, and Quantum Dynamics

2021 ◽  
Author(s):  
Yafu Guan ◽  
Changjian Xie ◽  
David R. Yarkony ◽  
Hua Guo
Keyword(s):  
Potential Energy ◽  
Excited States ◽  
First Principles ◽  
Quantum Dynamics ◽  
Chemical Processes ◽  
High Fidelity ◽  
Nonadiabatic Dynamics ◽  
Electronically Excited States ◽  
Electronically Excited ◽  
Oppenheimer Approximation

Nonadiabatic dynamics, which goes beyond the Born-Oppenheimer approximation, has increasingly been shown to play an important role in chemical processes, particularly those involving electronically excited states. Understanding multistate dynamics requires...

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