Energy decomposition analysis

Zhao, Lili; Hopffgarten, Moritz von; Andrada, Diego M.; Frenking, Gernot

doi:10.1002/wcms.1345

Cited by 458 publications

(446 citation statements)

References 198 publications

(324 reference statements)

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“…The computed reactivity trends will be analyzed in detail by means of the activation strain model (ASM) [11] of reactivity in combination with the energy decomposition analysis (EDA) method. [12] This methodology has been particularly helpful very recently to understand the factorsc ontrolling both the H 2 activation and the subsequent dihydrogen release into multiple bonds mediatedb yg eminal B/N FLPs. [13,14] Indeed, by means of this state-of-the-art approach we have proposed an orbital-controlled mechanism,c omplementary to the traditional mechanisms suggested by Pµpai et al [15] and Grimme et al, [16] where the degree of charge-transferc ooperativity betweent he key donor-acceptor orbitali nteractions, that is, LP(N)!s * (H 2 )a nd s(H 2 )!p p (B), alongt he reaction coordinate constitutes as uitablei ndicator of the reaction barrier.…”

Section: Introductionmentioning

confidence: 99%

Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH₂‐E′ Frustrated Lewis Pairs

Cabrera-Trujillo

Fernández

2018

Chemistry A European J

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The influence of the nature of the acid/base pairs on the reactivity of geminal frustrated Lewis pairs (FLPs) (Me2E‐CH2‐E′Ph2) has been computationally explored within the density functional theory framework. To this end, the dihydrogen‐activation reaction, one of the most representative processes in the chemistry of FLPs, has been selected. It is found that the activation barrier of this transformation as well as the geometry of the corresponding transition states strongly depend on the nature of the E/E′ atoms (E=Group 15 element, E′=Group 13 element) in the sense that lower barriers are associated with earlier transition states. Our calculations identify the geminal N/Al FLP as the most active system for the activation of dihydrogen. Moreover, the barrier height can be further reduced by replacing the phenyl group attached to the acidic atom by C6F5 or 3,5‐(CF3)2C6H3 (Fxyl) groups. The physical factors controlling the computed reactivity trends are quantitatively described in detail by means of the activation strain model of reactivity combined with the energy decomposition analysis method.

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Section: Introductionmentioning

confidence: 99%

Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH₂‐E′ Frustrated Lewis Pairs

Cabrera-Trujillo

Fernández

2018

Chemistry A European J

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“…Thus, to quantitatively analyze the relative contribution of the different energy components to the stability of C 6 H 6 , S 3 N 3 + and S 3 N 3 − as compared to C 6 H 6 4− , C 6 H 6 2− and S 3 N 3 3+ , we have carried out EDA analysis. The C−C and S−N single bond was fragmented homolytically in open‐shell singlet states for this purpose . Accordingly, for C 6 H 6 and S 3 N 3 3+ three open‐shell singlet C 2 H 2 and SN + fragments were chosen (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

6π, 8π and 10π Six Membered Sulfur Nitrogen Compounds: A Comparative Study with Organic Analogues

Sadik

Liya

2019

ChemistrySelect

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Benzene has played an important role in the development of the ideas concerning ′aromaticity′, as much as that benzene and its derivatives are the best examples of aromatic compounds. Although the inorganic aromatic compounds have been found to obey Hückel 4n+2 π electron rule, they often possess a different number of πe as compared to their organic analogues. One such system is cyclic compounds of S3N3, where 10 π aromatic S3N3− and 8π S3N3+ are known, but interestingly, a 6π benzene‐analogue of the sulfur‐nitrogen compound is not reported. Hence as a case study, we have undertaken an extensive theoretical investigation of the electronic structure of 6π, 8π and 10π electrons cyclic S3N33+, S3N3+ and S3N3−, based on the Energy Decomposition Analysis (EDA). We have also compared the results with isoelectronic classical C6H6, C6H62− and C6H64−. Our results indicated that the π‐contribution increases and the σ‐contribution decreases, while the contribution from the orbital interaction energy remains nearly similar upon addition of π electrons to C6H6 and S3N33+. However, the major decrease in the interaction energy is caused by the drastic reduction of the electrostatic component in C6H64− and S3N33+, which can be correlated to the instability of these molecules. Thus, aromatic binary compounds of sulfur and nitrogen are commonly π‐electron rich, while their aromatic hydrocarbon analogues are π‐electron precise.

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“…For a quantitative and qualitative interpretation of the chemical bond nature of cobalt oxides, an energy decomposition analysis (EDA), developed by Morokuma and by Ziegler and Rauk was employed. From EDA, the interaction energy of cobalt with the oxygens is decomposed in three terms defined to ΔE Pauli , ΔE elstat and ΔE orb , providing a chemically significant interpretation of chemical bonds …”

Section: Resultsmentioning

confidence: 99%

Methane Activation by (n=0, 1, 2; m= 1, 2): Reactivity Parameters, Electronic Properties and Binding Energy Analysis

et al. 2019

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The need for renewal and more efficient energy resources has led to a great interest in carrying out studies aiming to find novel sources of energy, which are able to supply the growing global demand, and providing an eco‐friendly usage of natural resources. In this context, the usage of methane stands out as a promising energetic alternative, mostly due to vast reserves, low cost and less polluting fuel. Theoretical studies with B3LYP, CCSD (t) and ZORA−B3LYP methods were used to look into the catalytic properties of (normalCnormalonormalOnormalmnormaln+ n= 0, 1, 2 and m=1, 2) in the methane C−H bond activation. According to the EDA results, the studied species presented two stabilizing factors for the global interaction energy, being the electrostatic ΔEelstat and orbital ΔEorb interactions. The HOMO and LUMO orbitals were also evaluated based on the molecular orbital diagrams for the monoxides and dioxides series. Regarding the oxidative insertion mechanism, the results demonstrate that the initial interaction between oxide and methane is of great relevance in its activation process, in which EBonding is benefited by the increasingly charge on the central metal. The high electron density regarding the oxides is meaningful for the reaction kinetics and the oxo ligands influence the thermodynamics of the reaction, becoming the DHA mechanism exergonic. Regarding the OHM mechanism, better kinetic conditions are found for CoO2++ and better thermodynamics for doubly charged cobalt monoxides and dioxides.

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Energy decomposition analysis

Cited by 458 publications

References 198 publications

Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH₂‐E′ Frustrated Lewis Pairs

Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH₂‐E′ Frustrated Lewis Pairs

6π, 8π and 10π Six Membered Sulfur Nitrogen Compounds: A Comparative Study with Organic Analogues

Methane Activation by (n=0, 1, 2; m= 1, 2): Reactivity Parameters, Electronic Properties and Binding Energy Analysis

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Energy decomposition analysis

Cited by 458 publications

References 198 publications

Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH2‐E′ Frustrated Lewis Pairs

Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH2‐E′ Frustrated Lewis Pairs

6π, 8π and 10π Six Membered Sulfur Nitrogen Compounds: A Comparative Study with Organic Analogues

Methane Activation by (n=0, 1, 2; m= 1, 2): Reactivity Parameters, Electronic Properties and Binding Energy Analysis

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Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH₂‐E′ Frustrated Lewis Pairs

Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH₂‐E′ Frustrated Lewis Pairs