Similarity and complementarity in chemistry

Bader, R. F. W.; Popelier, Paul L. A.; Chang, C.

doi:10.1016/0166-1280(92)85008-9

Cited by 85 publications

(63 citation statements)

References 44 publications

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“…The structure of the Laplacian of charge density for atoms in molecules is most easily visualized in terms of the minimum in ∇ 2 ρ(r), a polyhedron whose numbers of vertexes (V), edges (E), faces (F) and the only cage critical point within the sphere obey the Poincare-Hopf relationship [24]. As a peculiar case, this is easily transformed into Euler's polyhedral formula [25] V-E+F=2. Extrema in the Lapacian of ρ are classified by rank and signature in the same way as are critical points in the charge density.…”

Section: The Topological Analysis Of the Electronic Densitymentioning

confidence: 99%

From Metal Cluster to Metal Nanowire: A Topological Analysis of Electron Density and Band Structure Calculation

Chen

Mou

et al. 2002

IJMS

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Abstract:We investigate a theoretical model of molecular metalwire constructed from linear polynuclear metal complexes. In particular we study the linear Cr n metal complex and Cr molecular metalwire. The electron density distributions of the model nanowire and the linear Cr n metal complexes, with n = 3, 5, and 7, are calculated by employing CRYSTAL98 package with topological analysis. The preliminary results indicate that the bonding types between any two neighboring Cr are all the same, namely the polarized open-shell interaction. The pattern of electron density distribution in metal complexes resembles that of the model Cr nanowire as the number of metal ions increases. The conductivity of the model Cr nanowire is also tested by performing the band structure calculation.

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Section: The Topological Analysis Of the Electronic Densitymentioning

confidence: 99%

From Metal Cluster to Metal Nanowire: A Topological Analysis of Electron Density and Band Structure Calculation

Chen

Mou

et al. 2002

IJMS

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“…Both maps show contours at -V2p = 96.4 e k5 (4 au) around the sp2 atoms 0 1 3 and 017, on opposite sides with respect to the direction of the CO bond, and at about 120" from it. Such nonbonded valence charge concentrations correspond to the lone pairs for these atoms (1,50,51).…”

Section: The Conjugated System: Bond Ellipticity and Bond Overlapmentioning

confidence: 99%

“…Qualitative evidence about the electrophilic character of a given site can nevertheless be obtained from the values of the Laplacian function alone. A display of the reactive surjiace of the molecule, defined as the v2p = 0 isosurface, traces the separation between regions of charge concentration and charge depletion, and gives an effective description of the qualitative affinity of the various molecular portions toward Lewis acids and bases (1,51).…”

Section: Chemical Reactivity and The Molecular Reactive Surfacementioning

confidence: 99%

Charge density in crystalline citrinin from X-ray diffraction at 19 K

Roversi¹,

Merati²,

Destro³

et al. 1996

Can. J. Chem.

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For the fungal metabolite citrinin, CI3Hl4O5, the total experimental electron distribution p(r) and its Laplacian V2p(r) have been obtained from an extensive set (36 564 measurements) of single-crystal X-ray diffracted intensities at a temperature of 19 f 2 K. Relevant steps in data collection and processing are reported. The resulting 7698 independent intensity data have been analysed with a multipole (pseudoatoms) formalism. The topological properties of p(r) have been determined according to the quantum theory of atoms in molecules. CC and CO bond path lengths have been obtained by numerical integration; their values are found to be well correlated with those of the electron density at the bond critical points. Topological features have been used to characterize the extension of the conjugated system of the molecule, and to confirm the stability of its rings, particularly the two formed by intramolecular H bonds. Maps of V2p(r) are presented, showing details in the valence charge distribution and providing a very sensitive tool for analysing dependence of the density on the model adopted to interpret X-ray data. The known chemical reactivity of the molecule towards nucleophiles at a csp2 atom is confirmed by the shape of the molecular reactive surface (the zero envelope of V2p(r)).Key words: experimental electron density, low-temperature X-ray diffraction, topological analysis, Laplacian of p.Resume : En se basant sur un ensemble extensif (36 564 mesures) d'intensitks de diffraction des rayons X par un cristal unique obtenues i une tempkrature de 19 + 2 K, on a obtenu la distribution expkrimentale totale, p(r), ainsi que son laplacien, v2p(r), pour le mCtabolite de champignon citrinine, CI,H,,O5. On a ensuite analyst les 7698 donnCes indkpendantes d'intensitt k I'aide du formalisme multipble (pseudoatomes). On a determink les propriCtCs topologiques de p(r) suivant la thCorie quantique des atomes dans les molCcules. On a dCterminC les longueurs des liaisons CC et CO par leur inttgration numCrique; on a trouvt que leurs valeurs donnent une bonne corrilation avec celles obtenues i partir de la densite Clectronique des points critiques de liaison. On a utilisC des caractkristiques topologiques pour caractkriser l'extension du systtme conjuguC de la molCcule et pour confirmer la stabilitC de ses noyaux, particulibrement les deux formCs par les liaisons hydrogbnes intramoliculaires. On prisente des cartes de VZp(r) qui montrent les details de la distribution de charge de valence et qui fournissent un outil trbs sensible pour analyser la dtpendance de la densitC sur le modble adopt6 pour interpriter les donnCes de diffraction des rayons X. En se basant sur la forme de la surface molCculaire rCactive (l'enveloppe zCro du V2p(r)), on a confirm6 la rCactivitC connue de la molCcule vis-i-vis des nuclCophiles au niveau d'un atome de carbone sp2.Mots clis : densit6 klectronique expkrimentale, diffraction des rayons X ? I basse temptrature, diffraction, analyse topologique, laplacien de p.[Traduit par la rtdacti...

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“…11 The location of CPs in the Laplacian of the electron density, ƒ 2 , is relevant to the location of electron pairs 12 and to the support of the valence shell electron pair repulsion (VSEPR) model. 13 Critical points in ƒ 2 play a role in the context of molecular interaction, 14 i.e., in the formulation of a complementarity notion 15 in molecular alignment, in the prediction of angles of nucleophilic attack 16 and in studies on proton affinity. [17][18][19] Similarly, CPs in the Electron Localization Function (ELF) 20,21 are instrumental in, for example, the determination of protonation sites.…”

Section: Introductionmentioning

confidence: 99%

An improved algorithm to locate critical points in a 3D scalar field as implemented in the program MORPHY

Malcolm

Popelier

2003

J Comput Chem

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A new algorithm for location of the critical points in general scalar fields is described. The new method has been developed as part of an on-going process to exploit the topologic analysis of general 3D scalar fields. Part of this process involves the use of topologic information to seed the critical point search algorithm. The continuing move away from topologic studies of just the electron density requires more general algorithms and the ability to easily "plug in" new functions, for example, the Laplacian of the electron density ( triangle down (2)rho), the Electron Localisation Function (ELF), the Localised Orbital Locator (LOL), the Lennard-Jones function (LJF), as well as any new functions that may be proposed in the future. Another important aspect of the current algorithm is the retention of all possible intermediate information, for example, the paths describing the connectivity of critical points, as well as an ability to restart searches, something that becomes increasingly important when analysing larger systems. This new algorithm represents a core part of a new local version of the MORPHY code. We distinguish nine universal types of gradient paths.

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Similarity and complementarity in chemistry

Cited by 85 publications

References 44 publications

From Metal Cluster to Metal Nanowire: A Topological Analysis of Electron Density and Band Structure Calculation

From Metal Cluster to Metal Nanowire: A Topological Analysis of Electron Density and Band Structure Calculation

Charge density in crystalline citrinin from X-ray diffraction at 19 K

An improved algorithm to locate critical points in a 3D scalar field as implemented in the program MORPHY

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