Electron Pair Localization Function (EPLF) for Density Functional Theory and<i>ab Initio</i>Wave Function-Based Methods: A New Tool for Chemical Interpretation

Scemama, Anthony; Caffarel, Michel; Chaudret, Robin; Piquemal, Jean‐Philip

doi:10.1021/ct1005938

Cited by 17 publications

(16 citation statements)

References 28 publications

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“…Partial integration of the diagonal two‐particle reduced density matrix, contracted with a Gaussian test function analogous to eq. below, yields an electron pair localization function which can distinguish paired from unpaired electrons . Partitioning the one‐particle density matrix into pairs of domains

γ_{AB} (\overset{r}{true}, \overset{r^{'}}{true})

on atoms A and B provides additional insights into covalent bonding and electron sharing .…”

Section: Introductionmentioning

confidence: 99%

“…(2) below, yields an electron pair localization function which can distinguish paired from unpaired electrons. [37] Partitioning the one-particle density matrix into pairs of domains c AB ðr;r 0 Þ on atoms A and B provides additional insights into covalent bonding and electron sharing. [38][39][40] The Hilbert-space density matrix in localized basis sets is also widely used to quantify bond orders.…”

Section: Introductionmentioning

confidence: 99%

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Topological analysis of the electron delocalization range

Janesko

2016

J Comput Chem

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The electron delocalization range function EDR( r→;d) (Janesko et al., J. Chem. Phys. 2014, 141, 144104) quantifies the extent to which an electron at point r→ in a calculated wavefunction delocalizes over distance d. This work shows how topological analysis distills chemically useful information out of the EDR. Local maxima (attractors) in the EDR occur in regions such as atomic cores, covalent bonds, and lone pairs where the wavefunction is dominated by a single orbital lobe. The EDR characterizes each attractor in terms of a delocalization length D and a normalization N≤1, which are qualitatively consistent with the size of the orbital lobe and the number of lobes in the orbital. Attractors identify the progressively more delocalized atomic shells in heavy atoms, the interplay of delocalization and strong (nondynamical) correlation in stretched and dissociating covalent bonds, the locations of valence and weakly bound electrons in anionic water clusters, and the chemistry of different reactive sites on metal clusters. Application to ammonia dissociation over silicon illustrates how this density-matrix-based analysis can give insight into realistic systems. © 2016 Wiley Periodicals, Inc.

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γ_{AB} (\overset{r}{true}, \overset{r^{'}}{true})

on atoms A and B provides additional insights into covalent bonding and electron sharing .…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Topological analysis of the electron delocalization range

Janesko

2016

J Comput Chem

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“…Extension of the ELF/NCI approach is presently underway in the framework the 4-component fully relativistic framework as coupling of the Electron Pair Function (EPLF) 29 with NCI is also underway.…”

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confidence: 99%

Coupling Quantum Interpretative Techniques: Another Look at Chemical Mechanisms in Organic Reactions

Gillet

Chaudret

Contreras‐García

et al. 2012

J. Chem. Theory Comput.

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105

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A cross ELF-NCI analysis is tested over prototypical organic reactions. The synergetic use of ELF and NCI enables the understanding of reaction mechanisms since each method can respectively identify regions of strong and weak electron pairing. Chemically intuitive results are recovered and enriched by the identification of new features. Non covalent interactions are found to foresee the evolution of the reaction from the initial steps. Within NCI, no topological catastrophe is observed as changes are continuous to such an extent that future reaction steps can be predicted from the evolution of the initial NCI critical points. Indeed, strong convergences through the reaction paths between ELF and NCI critical points enable to identify key interactions at the origin of the bond formation. VMD scripts enabling the automatic generation of movies depicting the cross NCI/ELF analysis along a reaction path (or following a Born-Oppenheimer molecular dynamics trajectory) are provided as S.I.

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“…Future works will focus on the development of new potentialities to allow the analysis of other functions of interest for the bonding analysis such as the electron pair localization function [79] or other functions of interest in chemical reactivity such as the dual descriptor. [78] In addition, expanding the applicability to ELF grids implemented in other quantum chemistry program as the Car-Parrinello molecular dynamics package (CPMD) [80] is currently under development.…”

Section: Discussionmentioning

confidence: 99%

New insights in quantum chemical topology studies using numerical grid‐based analyses

Kozlowski

Pilmé

2011

J Comput Chem

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New insights in Quantum Chemical Topology of one-electron density functions have been proposed here by using a recent grid-based algorithm (Tang et al., J Phys Condens Matter 2009, 21, 084204), initially designed for the decomposition of the electron density. Beyond the charge analysis, we show that this algorithm is suitable for different scalar functions showing a more complex topology, that is, the Laplacian of the electron density, the electron localization function (ELF), and the molecular electrostatic potential (MEP). This algorithm makes use of a robust methodology enabling to numerically assign the data points of three-dimensional grids to basin volumes, and it has the advantage of requiring only the values of the scalar function without details on the wave function used to build the grid. Our implementation is briefly outlined (program named TopChem), its capabilities are examined, and technical aspects in terms of CPU requirement and accuracy of the results are discussed. Illustrative examples for individual molecules and crystalline solids obtained with gaussian and plane-wave-based density functional theory calculations are presented. Special attention was given to the MEP because its topological analysis is complex and scarce.

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Electron Pair Localization Function (EPLF) for Density Functional Theory andab InitioWave Function-Based Methods: A New Tool for Chemical Interpretation

Cited by 17 publications

References 28 publications

Topological analysis of the electron delocalization range

Topological analysis of the electron delocalization range

Coupling Quantum Interpretative Techniques: Another Look at Chemical Mechanisms in Organic Reactions

New insights in quantum chemical topology studies using numerical grid‐based analyses

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