Aspects of the Localizability of Electrons in Atoms and Molecules: Loge Theory and Related Methods

Aslangul, Claude; Constanciel, R.; Daudel, R.; Kottis, Ph.

doi:10.1016/s0065-3276(08)60542-0

Cited by 104 publications

(65 citation statements)

References 40 publications

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“…As remarked by Daudel et al: "Theories derived accordingly should provide the mathematical bridge between the chemical intuition and wave mechanics, which may be considered as a theoretical justification of the main chemical ideas." [37] It is well known that the electron density is of paramount importance to fully understand the ground-state properties of many-electron systems. As remarked by Yang et al: [38] "Interactions between electrons determine the structure and properties of matter from molecules to solids.…”

Section: Electron Density Q(r)mentioning

confidence: 99%

Unraveling reaction mechanisms by means of Quantum Chemical Topology Analysis

Andrés

González-Navarrete

Safont

2014

Int J of Quantum Chemistry

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A chemical reaction can be understood in terms of geometrical changes of the molecular structures and reordering of the electronic densities involved in the process; therefore, identifying structural and electronic density changes taking place along the reaction coordinate renders valuable information on reaction mechanism. Understanding the atomic rearrangements that occur during chemical reactions is of great importance, and this perspective aims to highlight the major developments in quantum chemical topology analysis, based on the combination of electron localization function and catastrophe theory as useful tools in elucidating the bonding and reactivity patterns of molecules. It reveals all the expected, but still ambiguous, elements of electronic structure extensively used by chemists. The chemical bonds determine chemical reactivity, and this technique offers the possibility of their visualization, allowing chemists to understand how atoms bond, how and where bonds are broken/ formed along a given reaction pathway at a most fundamental level, and so, better following and understanding the changes in the bond pattern. Their results clearly herald a new era, in which the atomic imaging of chemical bonds will constitute a new method for examining chemical structures and reaction mechanisms. The important feature of this procedure is that in practice the scope of its values is systemindependent. In addition, from a practical point of view, it is cheap to calculate and implement because wave functions are the required input, which are easily available from standard calculations. To capture these results two reaction mechanisms: isomerization of C(BH) 2 carbene and the thermal cycloheptatriene-norcaradiene isomerizations have been selected, indicating both the generality and utility of this type of analysis.

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Section: Electron Density Q(r)mentioning

confidence: 99%

Unraveling reaction mechanisms by means of Quantum Chemical Topology Analysis

Andrés

González-Navarrete

Safont

2014

Int J of Quantum Chemistry

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“…MPDs remind of Daudel's loges [21,22] which also use p ν (Ω ). There, the idea is to partition molecular space into domains, called "loges", and look for all different possibilities to distribute electrons into them.…”

Section: Similarities and Differencesmentioning

confidence: 99%

Understanding Maximum Probability Domains with Simple Models

Lopes

Braı̈da

Causa

et al. 2011

Advances in the Theory of Quantum Systems in Chemistry and Physics

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“…Daudel and co-workers (2)(3)(4) have reasoned that there should be some "best" decomposition of the physical space of a system into a number of mutually exclusive spaces, called loges. The "best" loges were to represent the most probable (in a quant~im mechanical sense) division of the physical space of the system into localized groups of electrons.…”

Section: Introductionmentioning

confidence: 99%

The Electron Pair in Chemistry

Daudel¹,

Bader²,

Stephens³

et al. 1974

Can. J. Chem.

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The reality of the electron pair as a fundamental unit in the electronic structure of molecular systems is evidenced by calc~llations which show that the most probable partitioning of a system is the one which localizes pairs of electrons in well-defined spatial regions or loges. The loges in turn, correspond to those regions of space generally associated with core, bonded, and nonbonded electrons. In terms of information theory, they yield the maximum amount of information concerning the localizability of the electrons. The most probable three-loge partitioning of the six-electron BH(XIZ+) system, for example, is dominated by the event which places two electrons in each of three loges, the location and shape of the loges being such as to justify the labelling of the electron pairs they localize as core, bonded and nonbonded. Since the loges are defined in real space and are totally nonoverlapping, one may define the volume of space occupied by pairs of electrons. In BH, for example, the volume of space required to contain 95% of the nonbonded pair of electrons is over two times larger than that required to contain 95% of the bonded pair. It is possible to define core loges which exhibit pair occupation probabilities ranging in value from 95% in LiH+ to 85% in BH. Corresponding probabilities ranging in value from 7 5 z to 90% are obtained for bonded and nonbonded loges. In the set of molecules studied here, the occurrence of events with such high probabilities is found only for loges which rnaximire the probability of a pair occupation.Le fait qile le doublet tlectronique est une unit6 fondamentale de la structure tlectronique de systemes moleculaires est Ctabli par des calculs qili rnontrent que la repartition la plus probable d'un systeme est celle qui localise les doublets Clectroniques dans des regions de I'espace bien definies 011 loges. Les loges aux electrons lies 011 non-lies, a leur tour correspondent a ces regions de I'espace generalement associees au noyau. Par rapport aux donnees de la theorie, on obtient le maximum de renseignements concernant la maniere de localiser les electrons. La repartition la plus probable en trois loges des six electrons du systtme BH ( X I Z + ) par exernple, est dominee par le cas qui place deux electrons dans chacune des trois loges; I'emplacement et la forme des loges sont tels qu'ils justifient la denomination des doublets electroniques, lies ou non-lies, et qu'ils les localisent comme noyau. Puisque les loges sont definies dans un espace reel et sont entierement sans recouvrement, on peut definir le volume de I'espace occupe par les doublets Clectroniques. Pour BH par exemple, le volume de I'espace necessaire pour contenir 95% dd'n doublet &lectronique non-lie depasse en importance, deux fois celui qui est necessaire pour contenir 95% d'un doublet electronique lit. 11 est possible de dtfinir des loges du noyau qui prtsentent des possibilites d'occupation d'un doublet de valeurs allant de 95% dans le L i H + a 85% dans le BH. Des probabilitks similaires de valeurs allan...

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Aspects of the Localizability of Electrons in Atoms and Molecules: Loge Theory and Related Methods

Cited by 104 publications

References 40 publications

Unraveling reaction mechanisms by means of Quantum Chemical Topology Analysis

Unraveling reaction mechanisms by means of Quantum Chemical Topology Analysis

Understanding Maximum Probability Domains with Simple Models

The Electron Pair in Chemistry

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