The reaction force constant as an indicator of synchronicity/nonsynchronicity in [4+2] cycloaddition processes

2013 ◽  
Vol 15 (19) ◽  
pp. 7311 ◽  
Author(s):  
Diana Yepes ◽  
Oscar Donoso-Tauda ◽  
Patricia Pérez ◽  
Jane S. Murray ◽  
Peter Politzer ◽  
...  
Keyword(s):  
Force Constant ◽  
Reaction Force ◽  
Reaction Force Constant

Perspectives on the reaction force constant

2013 ◽  
Vol 19 (10) ◽  
pp. 4111-4118 ◽  
Author(s):  
Peter Politzer ◽  
Jane S. Murray ◽  
Pablo Jaque
Keyword(s):  
Force Constant ◽  
Reaction Force ◽  
Reaction Force Constant

Effect of the exchange–correlation functional on the synchronicity/nonsynchronicity in bond formation in Diels–Alder reactions: a reaction force constant analysis

2019 ◽  
Vol 21 (14) ◽  
pp. 7412-7428 ◽  
Author(s):  
Diana Yepes ◽  
Joel Valenzuela ◽  
Jorge I. Martínez-Araya ◽  
Patricia Pérez ◽  
Pablo Jaque
Keyword(s):  
Force Constant ◽  
Bond Formation ◽  
Reaction Force ◽  
Diels Alder ◽  
Exchange Correlation ◽  
Reaction Force Constant

The performance of 24 KS-DFT-based methods (GGA, MGGA, HGGA, HMGGA, and DHGGA) was assessed, finding that M11 and M06-2X (HMGGA) predicting reliable TS geometries, energetics, and (a)synchronicities in Diels–Alder reactions.

Spectral Decomposition of the Reaction Force Constant

2020 ◽  
Vol 124 (12) ◽  
pp. 2372-2379 ◽  
Author(s):  
Felipe Urcelay ◽  
Alejandro Toro-Labbé ◽  
Soledad Gutiérrez-Oliva
Keyword(s):  
Force Constant ◽  
Spectral Decomposition ◽  
Reaction Force ◽  
Reaction Force Constant

The Position-Dependent Reaction Force Constant in Bond Dissociation/Formation

2008 ◽  
Vol 73 (6-7) ◽  
pp. 822-830 ◽  
Author(s):  
Peter Politzer ◽  
Jane S. Murray
Keyword(s):  
Force Constant ◽  
Dissociation Energy ◽  
Diatomic Molecules ◽  
Reaction Force ◽  
Bond Dissociation ◽  
Reaction Force Constant ◽  
Two Phases

The concept of a position-dependent reaction force constant κ(R) can be used to distinguish the two phases of bond dissociation or formation: stretched bond, κ(R) > 0, and interacting but separate fragments, κ(R) < 0. The transition between these phases is at κ(R) = 0, which coincides with the minimum (for dissociation) or maximum (for formation) of the reaction force. As was shown earlier, all of these occur (for diatomic molecules) at the separation R at which the system's energy relative to equilibrium is about 27% of its dissociation energy.

Intramolecular Proton Transfer in the Isomerization of Hydroxyacetone: A Detailed Characterization Based on Reaction Force Analysis and the Bond Fragility Spectrum

2020 ◽  
Author(s):  
Wallace Derricotte ◽  
Huiet Joseph
Keyword(s):  
Chemical Potential ◽  
Reaction Force ◽  
Intramolecular Proton Transfer ◽  
Intermediate Energy ◽  
Force Analysis ◽  
Activation Energy Barrier ◽  
Detailed Characterization ◽  
Proton Transfers ◽  
Reaction Force Constant

The mechanism of isomerization of hydroxyacetone to 2-hydroxypropanal is studied within the framework of reaction force analysis at the M06-2X/6-311++G(d,p) level of theory. Three unique pathways are considered: (i) a step-wise mechanism that proceeds through formation of the Z-isomer of their shared enediol intermediate, (ii) a step-wise mechanism that forms the E-isomer of the enediol, and (iii) a concerted pathway that bypasses the enediol intermediate. Energy calculations show that the concerted pathway has the lowest activation energy barrier at 45.7 kcal mol<sup>-1</sup>. The reaction force, chemical potential, and reaction electronic flux are calculated for each reaction to characterize electronic changes throughout the mechanism. The reaction force constant is calculated in order to investigate the synchronous/asynchronous nature of the concerted intramolecular proton transfers involved. Additional characterization of synchronicity is provided by calculating the bond fragility spectrum for each mechanism.

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