Investigation of electron density changes at the onset of a chemical reaction using the state-specific dual descriptor from conceptual density functional theory

2015 ◽  
Vol 17 (14) ◽  
pp. 9359-9368 ◽  
Author(s):  
Frank De Proft ◽  
Valérian Forquet ◽  
Benjamin Ourri ◽  
Henry Chermette ◽  
Paul Geerlings ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Transition State ◽  
Linear Combination ◽  
Electron Density ◽  
Chemical Reaction ◽  
Density Functional ◽  
The State ◽  
Dual Descriptor ◽  
Conceptual Density Functional Theory ◽  
Functional Theory

The electron density changes from reactants towards the transition state of a chemical reaction is expressed as a linear combination of the state-specific dual descriptors (SSDD) of the corresponding reactant complexes.

scholarly journals Unveiling the Different Reactivity of Bent and Linear Three-Atom-Components Participating in [3 + 2] Cycloaddition Reactions

Organics ◽  
2021 ◽  
Vol 2 (3) ◽  
pp. 274-286
Author(s):  
Mar Ríos-Gutiérrez ◽  
Luis R. Domingo ◽  
Fatemeh Ghodsi
Keyword(s):  
Density Functional Theory ◽  
Transition State ◽  
Electron Density ◽  
Density Functional ◽  
Geometrical Parameters ◽  
Single Bond ◽  
Conceptual Density Functional Theory ◽  
Functional Theory ◽  
Molecular Electron ◽  
Molecular Electron Density Theory

The reactivity of a series of pairs of bent and linear three-atom-component (B-TACs and L-TACs) participating in [3 + 2] cycloaddition (32CA) reactions towards ethylene and electrophilic dicyanoethylene (DCE) have been studied within the Molecular Electron Density Theory. While the pseudodiradical structure of B-TACs changes to that of pseudoradical or carbenoid L-TACs upon dehydrogenation, zwitterionic B-TACs remain unchanged. Conceptual Density Functional Theory (CDFT) indices characterize five of the nine TACs as strong nucleophiles participating in polar reactions towards electrophilic ethylenes. The activation energies of the 32CA reactions with electrophilic DCE range from 0.5 to 22.0 kcal·mol−1, being between 4.3 and 9.1 kcal·mol−1 lower than those with ethylene. In general, B-TACs are more reactive than their L-TAC counterparts. A change in the regioselectivity is found in these polar 32CA reactions; in general, while B-TACs are meta regioselective, L-TACs are ortho regioselective. The geometrical parameters of the transition state structures suggest that the formation of the single bond involving the most electrophilic carbon of DCE is more advanced. A change in the asynchronicity in the reactions involving B-TACs and L-TACs is also found.

Regaining the Woodward–Hoffmann rules for chelotropic reactions via conceptual DFT

2010 ◽  
Vol 88 (8) ◽  
pp. 858-865 ◽  
Author(s):  
Pablo Jaque ◽  
José V. Correa ◽  
Frank De Proft ◽  
Alejandro Toro-Labbé ◽  
Paul Geerlings
Keyword(s):  
Density Functional Theory ◽  
Wave Function ◽  
Density Functional ◽  
Pericyclic Reactions ◽  
Dual Descriptor ◽  
Conceptual Density Functional Theory ◽  
Functional Theory ◽  
Linear Path ◽  
Initial Hardness ◽  
Linear And Nonlinear

In our continuous effort to retrieve the Woodward–Hoffmann rules from conceptual density functional theory (DFT), we have examined the last type of pericyclic reactions, i.e., chelotropic reactions. Both the initial hardness response and the dual descriptor have been investigated to predict the allowed and forbidden character for the addition of SO2 to butadiene (4n system) and 1,3,5-hexatriene (4n + 2 system). It is shown that with both electronic descriptors, the conrotatory/disrotatory mode for the linear and nonlinear mechanisms are retrieved based on a density-only approach, free from consideration of orbital and (or) wave function symmetry. The dual descriptor moreover reveals that stabilizing interactions are presented only for the linear path, which can be considered as an overall favourable mechanism for a chelotropic reaction.

scholarly journals A statistical thermodynamics view of electron density polarisation: application to chemical selectivity

2020 ◽  
Vol 22 (41) ◽  
pp. 23553-23562
Author(s):  
Frédéric Guégan ◽  
Vincent Tognetti ◽  
Jorge I. Martínez-Araya ◽  
Henry Chermette ◽  
Lynda Merzoud ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Heat Exchange ◽  
Electron Density ◽  
Electrostatic Interactions ◽  
Density Functional ◽  
Statistical Thermodynamics ◽  
Conceptual Density Functional Theory ◽  
Functional Theory ◽  
Effective Work ◽  
Chemical Selectivity

A fundamental link between conceptual density functional theory and statistical thermodynamics is herein drawn, showing that intermolecular electrostatic interactions can be understood in terms of effective work and heat exchange.

scholarly journals Influence of Copper(I) Halides on the Reactivity of Aliphatic Carbodiimides

2020 ◽  
Vol 3 (1) ◽  
pp. 20
Author(s):  
Valentina Ferraro ◽  
Marco Bortoluzzi
Keyword(s):  
Density Functional Theory ◽  
Electronic Structure ◽  
General Formula ◽  
Electron Density ◽  
Density Functional ◽  
Functional Theory ◽  
Fukui Functions ◽  
Bond Lengths ◽  
Linear Complexes ◽  
Nitrogen Bond

The influence of copper(I) halides CuX (X = Cl, Br, I) on the electronic structure of N,N′-diisopropylcarbodiimide (DICDI) and N,N′-dicyclohexylcarbodiimide (DCC) was investigated by means of computational DFT (density functional theory) methods. The coordination of the considered carbodiimides occurs by one of the nitrogen atoms, with the formation of linear complexes having a general formula of [CuX(carbodiimide)]. Besides varying the carbon–nitrogen bond lengths, the thermodynamically favourable interaction with Cu(I) reduces the electron density on the carbodiimides and alters the energies of the (NCN)-centred, unoccupied orbitals. A small dependence of these effects on the choice of the halide was observable. The computed Fukui functions suggested negligible interaction of Cu(I) with incoming nucleophiles, and the reactivity of carbodiimides was altered by coordination mainly because of the increased electrophilicity of the {NCN} fragments.

Understanding the molecular mechanism of the stereoselective conversion of N-trialkylsilyloxy nitronates into bicyclic isoxazoline derivatives

2021 ◽  
Author(s):  
Agnieszka Kącka-Zych ◽  
Radomir Jasinski
Keyword(s):  
Density Functional Theory ◽  
Molecular Mechanism ◽  
Electron Density ◽  
Density Functional ◽  
Dft Method ◽  
Functional Theory ◽  
Molecular Electron ◽  
Molecular Electron Density Theory

Conversion of N-trialkylsilyloxy nitronates into bicyclic isoxazoline derivatives has been explored using Density Functional Theory (DFT) method within the context of the Molecular Electron Density Theory (MEDT) at the B97XD(PCM)/6-311G(d,p)...

Developing orbital-free quantum crystallography: the local potentials and associated partial charge densities

2021 ◽  
Vol 77 (4) ◽  
Author(s):  
Vladimir Tsirelson ◽  
Adam Stash
Keyword(s):  
Density Functional Theory ◽  
Electron Density ◽  
Density Functional ◽  
Electronic Energy ◽  
Physical Content ◽  
Functional Theory ◽  
Orbital Free ◽  
The One ◽  
Physical And Chemical ◽  
Quantum Crystallography

This work extends the orbital-free density functional theory to the field of quantum crystallography. The total electronic energy is decomposed into electrostatic, exchange, Weizsacker and Pauli components on the basis of physically grounded arguments. Then, the one-electron Euler equation is re-written through corresponding potentials, which have clear physical and chemical meaning. Partial electron densities related with these potentials by the Poisson equation are also defined. All these functions were analyzed from viewpoint of their physical content and limits of applicability. Then, they were expressed in terms of experimental electron density and its derivatives using the orbital-free density functional theory approximations, and applied to the study of chemical bonding in a heteromolecular crystal of ammonium hydrooxalate oxalic acid dihydrate. It is demonstrated that this approach allows the electron density to be decomposed into physically meaningful components associated with electrostatics, exchange, and spin-independent wave properties of electrons or with their combinations in a crystal. Therefore, the bonding information about a crystal that was previously unavailable for X-ray diffraction analysis can be now obtained.

A novel mechanism of spin-orientation dependence of O2 reactivity from first principles methods

2017 ◽  
Vol 7 (5) ◽  
pp. 1040-1044 ◽  
Author(s):  
M. C. S. Escaño ◽  
H. Kasai
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Transition State ◽  
First Principles ◽  
Density Functional ◽  
Orientation Dependence ◽  
Coupling Mechanism ◽  
Spin Moment ◽  
Spin Orientation ◽  
Functional Theory

A novel mechanism of oxygen reaction on a metal surface beyond the present charge transfer or hybridization mechanism, spin-orientation dependence via a coupling mechanism due to the finite spin moment of O2 at the transition state, is obtained using a combination of spin density functional theory (SDFT) and constrained DFT.

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