Toward triplet disilavinylidenes: A Hammett electronic survey for substituent effects on singlet‐triplet energy gaps of silylenes by DFT

Ayoubi‐Chianeh, Mojgan; Kassaee, M.Z.

doi:10.1002/poc.3988

Cited by 14 publications

(4 citation statements)

References 64 publications

(92 reference statements)

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“…However, the model has been used to describe many other properties like activation energies, orbital energies of metal organic complexes, or dipole moments . Furthermore, the model has been applied to nonbenzyl compounds. , The relation between Hammett constants and electronegativity has also been noted in the context of nucleo- and electrophilicity relevant for mechanistic discussions in organic chemistry . While Hammett’s model is very intuitive since it only requires separability of two dominating variables, its physical motivation has remained unclear …”

Section: Results and Discussionmentioning

confidence: 99%

Quantum Alchemy Based Bonding Trends and Their Link to Hammett’s Equation and Pauling’s Electronegativity Model

2023

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We present an intuitive and general analytical approximation estimating the energy of covalent single and double bonds between participating atoms in terms of their respective nuclear charges with just three parameters, [) ]. The functional form of our expression models an alchemical atomic energy decomposition between participating atoms A and B. After calibration, reasonably accurate bond dissociation energy estimates are obtained for hydrogen-saturated diatomics composed of p-block elements coming from the same row 2 ≤ n ≤ 4 in the periodic table. Corresponding changes in bond dissociation energies due to substitution of atom B by C can be obtained via simple formulas. While being of different functional form and origin, our model is as simple and accurate as Pauling's well-known electronegativity model. Analysis indicates that the model's response in covalent bonding to variation in nuclear charge is near-linear, which is consistent with Hammett's equation.

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Section: Results and Discussionmentioning

confidence: 99%

Quantum Alchemy Based Bonding Trends and Their Link to Hammett’s Equation and Pauling’s Electronegativity Model

2023

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“…Furthermore, the model has been applied to non-benzyl compounds. 35,38 The relation between Hammett constants and electronegativity has also been noted in the context of nucleo-and electro-philicity relevant for mechanistic discussions in organic chemistry. While Hammett's model is very intuitive since it only requires separability of two dominating variables, its physical motivation has remained unclear.…”

Section: Comparison To Hammett's Equationmentioning

confidence: 97%

From quantum alchemy to Hammett's equation: Revisiting the covalent bond

Sahre¹,

Rudorff²,

Lilienfeld³

2022

Preprint

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We present an intuitive and general analytical approximation estimating the energy of covalent single and double bonds between participating atoms in terms of their respective nuclear charges with just three parameters, [EAB ≈ a − bZAZB + c(ZThe functional form of our expression models an alchemical atomic energy decomposition between participating atoms A and B. After calibration, reasonably accurate bond energy estimates are obtained for hydrogen-saturated diatomics composed of p-block elements coming from the same row 2 ≤ n ≤ 4 in the periodic table. Corresponding changes in bond energies due to substitution of atom B by C can be obtained via simple formulas. While being of different functional form and origin, our model is as simple and accurate as Pauling's well-known electronegativity model. Analysis indicates that the model's response in covalent bonding to variation in nuclear charge is near-linear-which is consistent with Hammett's equation.

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“…Hammett's equation is notable for its simultaneous simplicity and predictive ability. [233][234][235][236][237] However, Hammett's original method is saddled with some significant disadvantages. The values of the substituent constants are highly dependent on the choice of reference reaction and may not be reliable for other reactions.…”

Section: δ-Ml For Activation Energy Predictionmentioning

confidence: 99%

“…Hammett's equation is notable for its simultaneous simplicity and predictive ability 233–237 . However, Hammett's original method is saddled with some significant disadvantages.…”

Section: For Activation Energiesmentioning

confidence: 99%

Machine learning activation energies of chemical reactions

Lewis‐Atwell

Townsend

Grayson

2021

WIREs Comput Mol Sci

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Application of machine learning (ML) to the prediction of reaction activation barriers is a new and exciting field for these algorithms. The works covered here are specifically those in which ML is trained to predict the activation energies of homogeneous chemical reactions, where the activation energy is given by the energy difference between the reactants and transition state of a reaction. Particular attention is paid to works that have applied ML to directly predict reaction activation energies, the limitations that may be found in these studies, and where comparisons of different types of chemical features for ML models have been made. Also explored are models that have been able to obtain high predictive accuracies, but with reduced datasets, using the Gaussian process regression ML model. In these studies, the chemical reactions for which activation barriers are modeled include those involving small organic molecules, aromatic rings, and organometallic catalysts. Also provided are brief explanations of some of the most popular types of ML models used in chemistry, as a beginner's guide for those unfamiliar.

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Toward triplet disilavinylidenes: A Hammett electronic survey for substituent effects on singlet‐triplet energy gaps of silylenes by DFT

Cited by 14 publications

References 64 publications

Quantum Alchemy Based Bonding Trends and Their Link to Hammett’s Equation and Pauling’s Electronegativity Model

Quantum Alchemy Based Bonding Trends and Their Link to Hammett’s Equation and Pauling’s Electronegativity Model

From quantum alchemy to Hammett's equation: Revisiting the covalent bond

Machine learning activation energies of chemical reactions

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