Hydrogenation and hydration of carbon dioxide: a detailed characterization of the reaction mechanisms based on the reaction force and reaction electronic flux analyses

Guzmán-Angel, Daniela; Gutiérrez‐Oliva, Soledad; Toro–Labbé, Alejandro

doi:10.1007/s00894-018-3891-5

Cited by 15 publications

(11 citation statements)

References 44 publications

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“…In previous theoretical studies, the reaction force has been interpreted in terms of the variation of atomic charges, bond orders and inter-atomic distances. [66][67][68][69][70] As we can notice, these three parameters are altogether present in the first-order expansions of F AB cl x ð Þ and F AB xc x ð Þ given by Eq. 20 and Eq.…”

Section: Additional Analysis Of Inter-atomic Reaction Forces From Bond Order Expansionsmentioning

confidence: 99%

Interacting Quantum Atoms Analysis of the Reaction Force: A Tool to Analyze Driving and Retarding Forces in Chemical Reactions

et al. 2021

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The analysis of the reaction force and its topology has provided a wide range of fruitful concepts in the theory of chemical reactivity over the years, allowing to identify chemically relevant regions along a reaction profile. The reaction force (RF), a projection of the Hellmann-Feynman forces acting on the nuclei of a molecular system onto a suitable reaction coordinate, is partitioned using the interacting quantum atoms approach (IQA). The exact IQA molecular energy decomposition is now shown to open a unique window to identify and quantify the chemical entities that drive or retard a chemical reaction. The RF/IQA coupling offers an extraordinarily detailed view of the type and number of elementary processes that take reactants into products, as tested on two sets of simple reactions.

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Section: Additional Analysis Of Inter-atomic Reaction Forces From Bond Order Expansionsmentioning

confidence: 99%

Interacting Quantum Atoms Analysis of the Reaction Force: A Tool to Analyze Driving and Retarding Forces in Chemical Reactions

et al. 2021

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“…A way to extract chemical information from the energy profile V (ξ) is through the reaction force defined as , F (ξ) is zero at the stationary points, negative before the TS having a minimum located at ξ min , and positive after the TS where it has a maximum at ξ max . In this context, {ξ min , ξ max } divides the reaction into three regions: the reactant region [ξ R , ξ min ] where reagents approach ξ R to reach other and structural changes predominate; the TS region [ξ min , ξ max ] where most electronic and structural changes occur; the product region [ξ max , ξ P ] where the system relaxes to reach the product of the reaction at ξ P . − …”

Section: Introductionmentioning

confidence: 99%

Spectral Decomposition of the Reaction Force Constant

2020

Self Cite

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Qualitative relationships between the reaction force constant κ(ξ), the second derivative of the potential energy V(ξ), and the reactive vibrational mode that drives the reaction in the transition state region have been used in the past to measure the synchronicity of key chemical events that lead a chemical reaction. In this work, we provide a formal demonstration that κ(ξ) can be expressed in terms of the frequencies of normal modes at each point of the reaction path. This produce a decomposition of κ(ξ) that is used to analyze few representatives chemical reactions, a series of intramolecular proton transfer on formic, thioformic and dithioformic acids, and an intermolecular double proton transfer in the HNS 2:H 2 O complex. It has been found that this partitioning allows to identify unambigously the reactive mode that drives the reaction at each point along the reaction coordinate thus giving relevant and detailed information about the mechanism of the chemical reactions under study.

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“…[48][49][50][51] Collectively, these properties represent a powerful toolkit for analyzing chemical reaction mechanisms and has been demonstrated in numerous studies. [52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70][71] The reaction force constant particularly has proven useful as an indicator of the synchronous/asynchronous nature of bond breaking/formation, it has been applied extensively to study synchronicity in Diels-Alder reactions. [72,73] Additionally, a recent method developed by Piotr Ordon and coworkers called the bond fragility spectrum aims to analyze the sequence of bond breaking/formation for a reaction by investigating the derivative of properties based on the molecular Hessian.…”

Section: Introductionmentioning

confidence: 99%

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

Joseph¹,

Derricotte²

2020

Preprint

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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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Hydrogenation and hydration of carbon dioxide: a detailed characterization of the reaction mechanisms based on the reaction force and reaction electronic flux analyses

Cited by 15 publications

References 44 publications

Interacting Quantum Atoms Analysis of the Reaction Force: A Tool to Analyze Driving and Retarding Forces in Chemical Reactions

Interacting Quantum Atoms Analysis of the Reaction Force: A Tool to Analyze Driving and Retarding Forces in Chemical Reactions

Spectral Decomposition of the Reaction Force Constant

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

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