ETS‐NOCV Decomposition of the Reaction Force: The HCN/CNH Isomerization Reaction Assisted by Water

Diaz, S.F.; Brela, Mateusz Z.; Gutiérrez‐Oliva, Soledad; Toro–Labbé, Alejandro; Michalak, Artur

doi:10.1002/jcc.24856

Cited by 22 publications

(20 citation statements)

References 65 publications

(116 reference statements)

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“…Further decomposition of the interaction part of the reaction force,

F_{i n t} (|, ξ)

into the ETS components was recently proposed by Díaz et al:

\frac{{d Δ E}_{i n t} (|, ξ)}{d ξ} = \frac{{d Δ E}_{P a u l i} (|, ξ)}{d ξ} + \frac{{d Δ E}_{e l s t a t} (|, ξ)}{d ξ} + \frac{d Δ E_{o r b} (|, ξ)}{d ξ}

F_{i n t} (|, ξ) = F_{P a u l i} (|, ξ) + F_{e l s t a t} (|, ξ) + F_{o r b} (|, ξ)

…”

Section: Methodsmentioning

confidence: 99%

“…Here,

F_{e l s t a t} (|, ξ)

is the electrostatic‐interaction force,

F_{P a u l i} (|, ξ)

is Pauli‐repulsion force, and

F_{o r b} (|, ξ)

is the orbital‐interaction force. It should be mentioned that the latter term can be further decomposed into the ETS‐NOCV components, following the NOCV decomposition of

Δ E_{o r b} (|, ξ)

term …”

Section: Methodsmentioning

confidence: 99%

“…It should be emphasized that a choice of the fragments may be not intuitive for all points on the pathway of a given chemical reaction. We have emphasized this difficulty in previous papers, discussing two different fragmentation schemes, leading to a description “from the reactant perspective” and “from the product perspective,” based on the partitioning “natural” to the reactants and products, respectively. It should be further stressed that depending on the fragmentation of the system (“reactant” or “product” perspective) the driving and retarding components can be included in different ETS‐NOCV reaction‐force terms as one partitioning is focused on the bond‐formation processes, while the other on bond‐breaking …”

Section: Methodsmentioning

confidence: 99%

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The influence of the metal cations and microhydration on the reaction trajectory of the N3 ↔ O2 thymine proton transfer: Quantum mechanical study

et al. 2017

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This study involves the intramolecular proton transfer (PT) process on a thymine nucleobase between N3 and O2 atoms. We explore a mechanism for the PT assisted by hexacoordinated divalent metals cations, namely Mg , Zn , and Hg . Our results point out that this reaction corresponds to a two-stage process. The first involves the PT from one of the aqua ligands toward O2. The implications of this stage are the formation of a hydroxo anion bound to the metal center and a positively charged thymine. To proceed to the second stage, a structural change is needed to allow the negatively charged hydroxo ligand to abstract the N3 proton, which represents the final product of the PT reaction. In the presence of the selected hexaaqua cations, the activation barrier is at most 8 kcal/mol. © 2017 Wiley Periodicals, Inc.

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“…Further decomposition of the interaction part of the reaction force,

F_{i n t} (|, ξ)

into the ETS components was recently proposed by Díaz et al:

\frac{{d Δ E}_{i n t} (|, ξ)}{d ξ} = \frac{{d Δ E}_{P a u l i} (|, ξ)}{d ξ} + \frac{{d Δ E}_{e l s t a t} (|, ξ)}{d ξ} + \frac{d Δ E_{o r b} (|, ξ)}{d ξ}

F_{i n t} (|, ξ) = F_{P a u l i} (|, ξ) + F_{e l s t a t} (|, ξ) + F_{o r b} (|, ξ)

…”

Section: Methodsmentioning

confidence: 99%

“…Here,

F_{e l s t a t} (|, ξ)

is the electrostatic‐interaction force,

F_{P a u l i} (|, ξ)

is Pauli‐repulsion force, and

F_{o r b} (|, ξ)

is the orbital‐interaction force. It should be mentioned that the latter term can be further decomposed into the ETS‐NOCV components, following the NOCV decomposition of

Δ E_{o r b} (|, ξ)

term …”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

The influence of the metal cations and microhydration on the reaction trajectory of the N3 ↔ O2 thymine proton transfer: Quantum mechanical study

et al. 2017

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“…These results demonstrate that any barrier of chemical transformation must originate from variations of all chemical bonding constituents and it is impossible to envision a priori which term will be of prime importance-to this end, quantum chemical analyses of bonding contributions in both substrates and transition states or even better along the entire reaction pathways (e.g. the powerful Activation Strain Model [65], the related approaches [66][67][68][69][70][71], as well as Electron Localization Function and Bonding Evolution Theory [72][73][74]) are in our view crucial for detailed understanding and more rational design of chemical reactions.…”

Section: Ets-nocv Analysismentioning

confidence: 99%

Formation of active species from ruthenium alkylidene catalysts—an insight from computational perspective

et al. 2019

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Ruthenium alkylidene complexes are commonly used as olefin metathesis catalysts. Initiation of the catalytic process requires formation of a 14-electron active ruthenium species via dissociation of a respective ligand. In the present work, this initiation step has been computationally studied for the Grubbs-type catalysts 3 ), using density functional theory (DFT). Additionally, the extended-transition-state combined with the natural orbitals for the chemical valence (ETS-NOCV) and the interacting quantum atoms (IQA) energy decomposition methods were applied. The computationally determined activity order within both families of the catalysts and the activation parameters are in agreement with reported experimental data. The significance of solvent simulation and the basis set superposition error (BSSE) correction is discussed. ETS-NOCV demonstrates that the bond between the dissociating ligand and the Ru-based fragment is largely ionic followed by the charge delocalizations: σ(Ru-P) and π(Ru-P) and the secondary CH … Cl, CH … π, and CH … HC interactions. In the case of transition state structures, the majority of stabilization stems from London dispersion forces exerted by the efficient CH … Cl, CH … π, and CH … HC interactions. Interestingly, the height of the electronic dissociation barriers is, however, directly connected with the prevalent (unfavourable) changes in the electrostatic and orbital interaction contributions despite the favourable relief in Pauli repulsion and geometry reorganization terms during the activation process. According to the IQA results, the isopropoxy group in the Hoveyda-Grubbs-type catalysts is an efficient donor of intra-molecular interactions which are important for the activity of these catalysts.

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“…In this approach, the terms associated with the structural deformation of the reactants (strain, deformation) and the interaction between the chemical fragments are considered. In a recent article [ 16 ], we proposed to further decompose the interaction component of the reaction force, based on the Ziegler–Rauk energy decomposition scheme ( extended transition state , ETS; energy decomposition analysis , EDA) [ 17 – 19 ] and the extended-transition-state natural orbitals for chemical valence (ETS-NOCV) approach [ 20 ]; the ETS-NOCV decomposition of the reaction force was used in analysis of the water assisted HCN/CNH isomerization [ 16 ], and in the metal-assisted intra-molecular proton transfer in thymine [ 21 ].…”

Section: Introductionmentioning

confidence: 99%

ETS-NOCV decomposition of the reaction force for double-proton transfer in formamide-derived systems

2017

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The analysis of the electronic-structure changes along IRC paths for double-proton-transfer reactions in the formamide dimer (R1), formamide–thioformamide system (R2), and the thioformamide dimer (R3) was performed based on the extended-transition-state natural orbitals for chemical valence (ETS-NOCV) partitioning of the reaction force, considering the intra-fragments strain and the inter-fragments interaction terms, and further—the electrostatic, Pauli-repulsion and orbital interaction components, with the latter being decomposed into the NOCV components. Two methods of the system partitioning into the fragments were considered (‘reactant perspective’/bond-formation, ‘product perspective’ / bond-breaking). In agreement with previous studies, the results indicate that the major changes in the electronic structure occur in the transition state region; the bond-breaking processes are, however, initiated already in the reactant region, prior to entering the TS region. The electrostatic contributions were identified as the main factor responsible for the increase in the activation barrier in the order R1 < R2 < R3.Electronic supplementary materialThe online version of this article (10.1007/s00894-017-3564-9) contains supplementary material, which is available to authorized users.

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ETS‐NOCV Decomposition of the Reaction Force: The HCN/CNH Isomerization Reaction Assisted by Water

Cited by 22 publications

References 65 publications

The influence of the metal cations and microhydration on the reaction trajectory of the N3 ↔ O2 thymine proton transfer: Quantum mechanical study

The influence of the metal cations and microhydration on the reaction trajectory of the N3 ↔ O2 thymine proton transfer: Quantum mechanical study

Formation of active species from ruthenium alkylidene catalysts—an insight from computational perspective

ETS-NOCV decomposition of the reaction force for double-proton transfer in formamide-derived systems

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