Electron pairing and chemical bonds: Pair localization in ELF domains from the analysis of domain averaged Fermi holes

Ponec, Robert; Chaves, Joaquin

doi:10.1002/jcc.20465

Cited by 12 publications

(9 citation statements)

References 41 publications

(54 reference statements)

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“…[47] Ponec and Chaves have addressed this problem by analyzing domain-averaged Fermi holes. [52] They concluded that the explanation lies in the determination of basin boundaries, and contamination by electrons in neighboring domains.…”

Section: Defining the Lone Pair Domainmentioning

confidence: 99%

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Quantifying the Nature of Lone Pair Domains

Rahm

2013

ChemPhysChem

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The lone pair lies at the heart of chemistry, and is often in a conceptual respect the site of chemical reactivity. Here we show how the analysis of the electron localization function (ELF) can be improved upon by introducing intra-basin partitioning. The high-ELF localization domain population (HELP), is presented as a probe of the more chemically relevant and electron-localized regions of the ELF lone pair basin, and shown to correlate with a range of physical properties and quantum mechanical constructs, such as the ESP, e and H(+) affinity, IP, HOMO/LUMO energies, atomic charge, NBO lone pair orbitals, and molecular geometry. A strong connection between topological density and orbital-based analysis of chemistry is intuitively expected, yet this is the first time that an average electron population, obtained by any localization method, can be linked to properties of molecules. The application of HELP as a descriptor of lone pair domains is predicted to be of general use.

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Section: Defining the Lone Pair Domainmentioning

confidence: 99%

“…one electron) in a non-infinitesimal volume of space (e.g. [52] They concluded that the explanation lies in the determination of basin boundaries, and contamination by electrons in neighboring domains. This is because many electrons contribute to the average population.…”

Section: Introductionmentioning

confidence: 99%

Quantifying the Nature of Lone Pair Domains

Rahm

2013

ChemPhysChem

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“…N 2 is a textbook example for the triple bond. Nevertheless, the topological analysis of the ELF gives a population close to four electrons in the NN bond, which does not correspond to the common Lewis structure17. Here, we searched for the domains maximizing the probabilities of finding three up and three down electrons between the two nuclei, following the traditional σ/π interpretation of the bond.…”

Section: Applicationsmentioning

confidence: 99%

Maximum probability domains from Quantum Monte Carlo calculations

2006

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Abstract:Although it would be tempting to associate the Lewis structures to the maxima of the squared wave function | | 2 , we prefer in this paper the use of domains of the three-dimensional space, which maximize the probability of containing opposite-spin electron pairs. We find for simple systems (CH 4 , H 2 O, Ne, N 2 , C 2 H 2 ) domains comparable to those obtained with the electron localization function (ELF) or by localizing molecular orbitals. The different domains we define can overlap, and this gives an interesting physical picture of the floppiness of CH + 5 and of the symmetric hydrogen bond in FHF − . The presence of multiple solutions has an analogy with resonant structures, as shown in the trans-bent structure of Si 2 H 2 . Correlated wave functions were used (MCSCF or Slater-Jastrow) in the Variational Quantum Monte Carlo framework.

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“…The ELF population analysis often yields basin populations close to the integer values expected from the Lewis model; however the deviations from even integers have been interpreted by some authors as a deficiency of the partition scheme [64,65]. In the mesomery model, the charge distribution is represented by a superposition of weighted structures, the ELF populations and population covariances enable therefore to estimate the weights of the considered structures [66,67]; moreover the electron number probabilities provide additional pieces of information about the electron delocalization.…”

Section: The Elf Population Analysismentioning

confidence: 97%

The Relevance of the ELF Topological Approach to the Lewis, Kossel, and Langmuir Bond Model

Silvi

2015

The Chemical Bond II

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The electron localization function (ELF) approach to chemical bonding is revisited as a tool to check the falsifiability of the Lewis hypotheses. It is shown that the boundaries of the ELF basins correspond to zero-flux surfaces of the local integrated same spin pair probability enabling the determination of regions of the molecular space which maximizes the opposite spin pair density and therefore groups of electrons. The ELF yields a partition into core and valence basins which matches the Lewis model. The valence basins which correspond either to electron lone pairs or to bonds enable the definition of atomic valence shells in which bonding basins are shared by at least two atomic valence shells. The ELF basin populations take into account the mesomery which explains the deviations from ideal values. The organization of the basins around the atomic cores often complies with the VSEPR rules. The behavior of the ELF basins upon deformation of the nuclear frame sheds light onto the reactivity and reaction mechanisms, whereas the basin compressibilities provide chemical explanations of pressureinduced phase transitions.

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Electron pairing and chemical bonds: Pair localization in ELF domains from the analysis of domain averaged Fermi holes

Cited by 12 publications

References 41 publications

Quantifying the Nature of Lone Pair Domains

Quantifying the Nature of Lone Pair Domains

Maximum probability domains from Quantum Monte Carlo calculations

The Relevance of the ELF Topological Approach to the Lewis, Kossel, and Langmuir Bond Model

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