Chemical reactivity indexes in density functional theory

Chermette, Henry

doi:10.1002/(sici)1096-987x(19990115)20:1<129::aid-jcc13>3.3.co;2-1

Cited by 298 publications

(486 citation statements)

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“…5,6 In contrast with molecular electronic (conductance) measurements, where, in general, molecules of interest must bridge between two biased electrodes, CS constitutes a frequency-dependent single probe measurement. 4,[12][13][14][15][16][17][18] This is the so-called conceptual DFT (also known as chemical or chemical reactivity DFT) 4,12-18 that was developed from the 1980's onwards and is inspired by the work of Robert Parr and coworkers. Statistically, for a distribution of redox states thermally equilibrated with an electron bath, i.e.…”

Section: Capacitance Spectroscopymentioning

confidence: 99%

“…It should be noted here (see ESI, † 3, particularly eqn (S27)) that e 2 /C q (N) = e N+1 À e N for an isolated N-electron system (e.g. The electronic wave function (calculated from the DFT method) describing this redox active metalmolecule interface mathematically can lead to a continuum function [eqn (18) equates to (14) in this case] known as density of states (DOS) and then C q (N) is directly proportional to the DOS formed by redox states tethered to the electrode. The implications inherent within eqn (18) are electrochemically significant; the quantum term of the redox capacitance is implicitly given by the difference between e N+1 (corresponding to the LUMO energy state of a redox active molecule) and e N (corresponding to the HOMO energy state of a redox active molecule) energies.…”

Section: Capacitance Spectroscopy and Density Functional Theorymentioning

confidence: 99%

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Capacitance spectroscopy and density functional theory

Bueno

Feliciano

Davis

2015

Phys. Chem. Chem. Phys.

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The redox capacitance and its associated quantum component arising from the charging of molecular levels from coupled metallic states are resolvable and quantified experimentally by capacitance spectroscopy (CS). Herein we relate both this N-electron system capacitance directly to conceptual chemistry density functional theory (DFT) and the charging magnitude and associated quantum capacitive term (which resemble those introduced by Serge Luryi) to the Kohn-Sham frontier molecular orbital associated energies for isolated molecules and DFT calculated redox density of states (DOS) at metal-molecule junctions for a single molecule and molecular films confined at metallic interfaces. DFT computational analyses reveal the orbital energetic alignment between the iron redox site and those states in the metal specifically when metal-molecule junctions are formed. The impact of this on the resolved chemical softness and capacitance is also revealed. These analyses, additionally, are shown to numerically resolve redox capacitance in a manner that accurately reproduces experimental observations for molecular films. These observations both theoretically underpin CS and provide guidance on its optimised application in interfacial analyses involving molecular electrochemistry and derived sensory applications.

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Section: Capacitance Spectroscopymentioning

confidence: 99%

Section: Capacitance Spectroscopy and Density Functional Theorymentioning

confidence: 99%

Capacitance spectroscopy and density functional theory

Bueno

Feliciano

Davis

2015

Phys. Chem. Chem. Phys.

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“…Although the hard/soft acid/base (HSAB) principle was originally empirically motivated, 1-4 the development of the density functional reactivity theory (also called conceptual DFT) [5][6][7][8][9][10][11] allowed the HSAB principle, at least in its global form, to be theoretically explored and justified. [12][13][14][15][16][17][18][19] The key insights here were obtained by Parr and Pearson, who proposed a quantitative measure for the chemical hardness, namely the second derivative of the energy with respect to the number of electrons, at fixed geometry: 20…”

Section: Motivationmentioning

confidence: 99%

The unconstrained local hardness: an intriguing quantity, beset by problems

Cuevas-Saavedra

Rabi

Ayers

2011

Phys. Chem. Chem. Phys.

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Developing a mathematical approach to the local hard/soft acid/base principle requires an unambiguous definition for the local hardness. One such quantity, which has aroused significant interest in recent years, is the unconstrained local hardness. Key identities are derived for the unconstrained local hardness, δμ/δρ(r). Several identities are presented which allow one to determine the unconstrained local hardness either explicitly using the hardness kernel and the inverse-linear response function, or implicitly by solving a system of linear equations. One result of this analysis is that the problem of determining the unconstrained local hardness is infinitely ill-conditioned because arbitrarily small changes in electron density can cause enormous changes in the chemical potential. This is manifest in the exponential divergence of the unconstrained local hardness as one moves away from the system. This suggests that one should be very careful when using the unconstrained local hardness for chemical interpretation.

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“…31 Finally, various reactivity descriptors and their application in understanding of chemical reactivity of molecules have been reported in the framework of DFT. 32,33 In the¯rst part of present research, the aim is to obtain the structural information and electronic features of the most stable dactylyne stereoisomers by applying DFT based global reactivity descriptor such as the global softness ðSÞ, the chemical potential (), the electrophilicity index ð!Þ, and also dipole moment. In the second part of work, we have investigated the in°uences of some electron donor and withdrawing substituents on the dactylyne reactivity descriptors.…”

Section: Introductionmentioning

confidence: 99%

A Theoretical Study of Dactylyne Stereoisomers: A Marine Natural Product From Aplysia Dactylomela

Farrokhnia

Nabipour

Bargahi

2012

J. Theor. Comput. Chem.

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Dactylyne is an acetylenic dibromochloro ether from the Persian Gulf sea hare, Aplysia dactylomela. As a result of its unique structure and nontoxic nature; it has been known as a promising pharmacological substance of marine origin. A theoretical study of dactylyne and its stereoisomers, initiated in the hope of understanding more details of its action, is reported here. In the present research, for the¯rst time, a density functional theory (DFT) calculation has been performed on the stereoisomers of dactylyne to determine the most stable con¯gurations in gas phase. The HOMOÀLUMO gap, global softness, chemical potential, and electrophilicity index have been calculated for the most stable stereoisomers at the B3LYP level of theory. These DFT-based global reactivity descriptors have been applied to demonstrate the reactive nature of compounds. Moreover, results from the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis have been employed to support the¯nding of more reactive stereoisomers. The investigation has indicated that the con¯guration of stereoisomers has some e®ects on their electronic and structural properties which control their global reactivity. It is also shown that the most probable interaction sites of dactylyne are in its unsaturated region. In the second part of our study, the e®ects of some typical substituents on dactylyne reactivity have been investigated theoretically and it has been shown that the strong electron donor groups increase the reactivity of dactylyne more than withdrawing substituent. However, creation of an ionic compound highly in°uences on reactivity descriptors.

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Chemical reactivity indexes in density functional theory

Cited by 298 publications

References 0 publications

Capacitance spectroscopy and density functional theory

Capacitance spectroscopy and density functional theory

The unconstrained local hardness: an intriguing quantity, beset by problems

A Theoretical Study of Dactylyne Stereoisomers: A Marine Natural Product From Aplysia Dactylomela

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