scholarly journals Bimolecular reactions observed by femtosecond detachment to aligned transition states: Inelastic and reactive dynamics

1996 ◽  
Vol 105 (17) ◽  
pp. 7864-7867 ◽  
Author(s):  
Dongping Zhong ◽  
P. Y. Cheng ◽  
Ahmed H. Zewail
Keyword(s):  
Transition States ◽  
Bimolecular Reactions ◽  
Reactive Dynamics

scholarly journals Morse bifurcations of transition states in bimolecular reactions

Nonlinearity ◽  
2015 ◽  
Vol 28 (12) ◽  
pp. 4303-4329 ◽  
Author(s):  
R S MacKay ◽  
D C Strub
Keyword(s):  
Transition States ◽  
Bimolecular Reactions

Organic reactions in liquid crystalline solvents. 2. An investigation into the use of liquid crystalline solvents to effect stereochemical control in the Diels–Alder reaction

1985 ◽  
Vol 63 (10) ◽  
pp. 2736-2741 ◽  
Author(s):  
William J. Leigh
Keyword(s):  
Liquid Crystalline ◽  
Transition States ◽  
Alder Reaction ◽  
Diels Alder ◽  
Shape Transition ◽  
Bimolecular Reactions ◽  
Solvent Phase ◽  
Stereochemical Control ◽  
Diels Alder Reaction ◽  
Liquid Crystalline Phases

The possibility of using liquid crystalline solvents to control the stereospecificity of bimolecular reactions as a result of differences in liquid crystalline solvation of the various possible transition states has been examined. The Diels–Alder reactions of 2,5-dimethyl-3,4-diphenylcyclopentadienone with four dienophiles of varying steric size (cyclopentene, cycloheptene, indene, and acenaphthylene) have been carried out in benzene, cholesteryl nonanoate (isotropic), cholesteryl propionate (cholesteric), and 4-ethyl-4′-(4-pentylcyclohexyl)biphenyl (smectic) at 105 °C. In spite of very large differences in steric solvation requirements for the endo- (globular in shape) and exo- (plate-like in shape) transition states in these reactions, no variation in product ratio with solvent phase is observed in any case.The inability of the ordered liquid crystalline phases to differentiate between endo- and exo-transition states in the Diels–Alder reactions investigated is rationalized as being the possible result of several factors. The most important of these are believed to be free volume effects, owing to both inefficient steric solvation of the bulky diene and volume contraction in the transition states for cycloaddition.

Confined molecules: experiment meets theory in small spaces

2020 ◽  
Vol 53 ◽  
Author(s):  
Yang Yu ◽  
Julius Rebek
Keyword(s):  
Magnetic Properties ◽  
Small Molecules ◽  
Data Storage ◽  
Transition States ◽  
Reactive Species ◽  
Bimolecular Reactions ◽  
Limited Space ◽  
Potential Applications

Abstract The behavior of molecules confined to small spaces is fascinating chemistry and lies at the heart of signaling processes in biology. Our approach to confinement is through reversible encapsulation of small molecules in synthetic containers. We show that confinement leads to amplified reactivities in bimolecular reactions, stabilization of otherwise reactive species, and limitation in motions that create new stereochemical arrangements. The isolation of molecules from solvent makes for manageable computations and has stimulated theorist to examine reaction details in the limited space. Transition states for reactions and rearrangements can be calculated, the effects of (de)solvation can be evaluated and the magnetic properties of the containers can be compared with experimental observations. Finally, we outline several potential applications, including entanglement chemistry and the use of isomers in data storage.

Incorporation of Reactive Dynamics in Simulations of Chemically-Sustained Shock Waves

1989 ◽  
Author(s):  
Donald W. Brenner ◽  
Mark L. Elert ◽  
C. T. White
Keyword(s):  
Shock Waves ◽  
Reactive Dynamics

Theoretical Computations on the Pyrolysis of Alkyl (dithio)acetates

2020 ◽  
Vol 17 (3) ◽  
pp. 224-233
Author(s):  
Xun Zhu ◽  
Chen Jian ◽  
Xiuqin Zhou ◽  
Abdullah M. Asiri ◽  
Khalid A. Alamry ◽  
...  
Keyword(s):  
Transition States ◽  
Membered Ring ◽  
Pyrolysis Process ◽  
Alkyl Esters ◽  
Charge Distributions ◽  
Theoretical Analyses

The pyrolysis of methyl alkyl esters I to III and dithioesters IV to VI were theoretically calculated. All possible pyrolysis paths were considered. Both esters and dithioesters presented three potential paths via six-, four- and five-membered ring transition states, respectively. The calculation processes were calculated using MP2/6-31G(d) set. In-depth theoretical analyses were also presented, including NBO related analyses, synchronicities, and charge distributions, to reveal the detailed pyrolysis process.

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