scholarly journals Curly arrows meet electron density transfers in chemical reaction mechanisms: from electron localization function (ELF) analysis to valence-shell electron-pair repulsion (VSEPR) inspired interpretation

2016 ◽  
Vol 52 (53) ◽  
pp. 8183-8195 ◽  
Author(s):  
Juan Andrés ◽  
Sławomir Berski ◽  
Bernard Silvi
Keyword(s):  
Electron Density ◽  
Chemical Reactions ◽  
Chemical Reaction ◽  
Reaction Mechanisms ◽  
Electron Pair ◽  
Reaction Path ◽  
Electron Localization ◽  
Valence Shell ◽  
Localization Function ◽  
Chemical Reaction Mechanisms

The displacement of the nuclei along the reaction path provides an explanatory interpretation of the electron density transfers making possible to understand chemical reactions.

A Paramedic Treatment for Modeling Explicitly Solvated Chemical Reaction Mechanisms

2018 ◽  
Author(s):  
Yasemin Basdogan ◽  
John Keith
Keyword(s):  
Reaction Mechanism ◽  
Chemical Reaction ◽  
Reaction Mechanisms ◽  
Reaction Pathway ◽  
Optimization Procedure ◽  
Cost Effective ◽  
Chemical Reaction Mechanisms ◽  
Solvent Molecules ◽  
Dynamics Simulations ◽  
Mbh Reaction

<div> <div> <div> <p>We report a static quantum chemistry modeling treatment to study how solvent molecules affect chemical reaction mechanisms without dynamics simulations. This modeling scheme uses a global optimization procedure to identify low energy intermediate states with different numbers of explicit solvent molecules and then the growing string method to locate sequential transition states along a reaction pathway. Testing this approach on the acid-catalyzed Morita-Baylis-Hillman (MBH) reaction in methanol, we found a reaction mechanism that is consistent with both recent experiments and computationally intensive dynamics simulations with explicit solvation. In doing so, we explain unphysical pitfalls that obfuscate computational modeling that uses microsolvated reaction intermediates. This new paramedic approach can promisingly capture essential physical chemistry of the complicated and multistep MBH reaction mechanism, and the energy profiles found with this model appear reasonably insensitive to the level of theory used for energy calculations. Thus, it should be a useful and computationally cost-effective approach for modeling solvent mediated reaction mechanisms when dynamics simulations are not possible. </p> </div> </div> </div>

Models and Explanations: Understanding Chemical Reaction Mechanisms

2000 ◽  
Author(s):  
Barry K. Carpenter
Keyword(s):  
Internal Rotation ◽  
Chemical Reaction ◽  
Reaction Mechanisms ◽  
Second Law Of Thermodynamics ◽  
The Other ◽  
Second Law ◽  
Original Design ◽  
Mechanical Analogy ◽  
Boston College ◽  
Chemical Reaction Mechanisms

In 1997, Ross Kelly and his coworkers at Boston College reported their results from an experiment with an intriguing premise (Kelly et al., 1997; see also Kelly et al., 1998). They had synthesized the molecule shown in figure 12.1. It was designed to be a “molecular ratchet,” so named because it appeared that it should undergo internal rotation about the A—B bond more readily in one direction than the other. The reason for thinking this might occur was that the benzophenanthrene moiety—the “pawl” of the ratchet—was anticipated to be helical. Thus, in some sense, this might be an inverse ratchet where the asymmetry dictating the sense of rotation would reside in the pawl rather than in the “teeth” on the “wheel” (the triptycene unit) as it does in a normal mechanical ratchet. Kelly and coworkers designed an elegant experiment to determine whether their molecular ratchet was functioning as anticipated, and they were (presumably) disappointed to find that it was not—internal rotation about the A—B bond occurred at equal rates in each direction. In 1998 Davis pointed out that occurrence of the desired behavior of the molecular ratchet would have constituted a violation of the second law of thermodynamics (Davis, 1998). With hindsight, I think most chemists would agree that Davis’s critique is unassailable, although the appeal of the mechanical analogy was so strong that I imagine those same chemists would also understand if Kelly et al. had overlooked the thermodynamic consequences of their proposal in the original design of the experiment. But now comes the interesting question: Suppose Kelly et al. had been fully aware that their experiment, if successful, would undermine the second law of thermodynamics, should they have conducted it anyway? Davis, in his critique writes: . . .Some would argue that this experiment was misconceived. To challenge the Second Law may be seen as scientific heresy (a nice irony, considering the Jesuit origins of Boston College), and the theoretical arguments against molecular ratchets and trapdoors are well developed. . . .

scholarly journals Reduced chemical reaction mechanisms for simulating sodium emissions by solid-fuel combustion

2020 ◽  
Vol 1-4 ◽  
pp. 100009
Author(s):  
Kaidi Wan ◽  
Luc Vervisch ◽  
Zhenxun Gao ◽  
Pascale Domingo ◽  
Chongwen Jiang ◽  
...  
Keyword(s):  
Chemical Reaction ◽  
Solid Fuel ◽  
Reaction Mechanisms ◽  
Fuel Combustion ◽  
Solid Fuel Combustion ◽  
Chemical Reaction Mechanisms
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