One-electron bonds are not “half-bonds”

Sousa, David Wilian Oliveira de; Nascimento, Marco Antônio Chaer

doi:10.1039/c9cp02209k

Cited by 23 publications

(23 citation statements)

References 100 publications

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“…These results, classify the NaÀB bond in NaBH 3 À as a one-electron bond. [21] Figure S1 provides additional evidence that justifies our assumption that B À H ELF basins overlap de extreme lobe of the boron porbital. For radical CBH 3 À at NaBH 3 À equilibrium structure, ELF identifies the three BÀH basins and two monosynaptic basins on the main axis, one above and one below the BH 3 moiety.…”

supporting

confidence: 72%

Neither too Classic nor too Exotic: One‐Electron Na⋅B Bond in NaBH₃⁻ Cluster

2021

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It is here reported that the NaBH 3 À cluster exhibits a Na•B one-electron bond, a well-established type of electrondeficient bonding in the literature. The topological analysis of the electron localization function, at the correlated level, reveals that Na À , when approaching the bonding distance, fairly distributes its valence electron pair between two lobes. One of these electrons is used to bond with BH 3 , which participates through its boron empty p-orbital. Furthermore, the bonding situation of LiBH 3 À , KBH 3 À , MgBH 3 , and CaBH 3 global minima structures are similar to that of NaBH 3 À , extending the family of these new one-electron bond systems with biradicaloid character.

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supporting

confidence: 72%

Neither too Classic nor too Exotic: One‐Electron Na⋅B Bond in NaBH₃⁻ Cluster

2021

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“…The PBI for each of the three pairs is equal to 0.5, indicating that each corresponds to exactly half of a covalent bond. The analysis results indicate that there is one ordinary σ‐bond and a one‐electron π‐bond between the two BH 2 moieties, consistent with previous reports and also the spin density plot showing clear π‐bonding feature.…”

Section: Advanced Examplesmentioning

confidence: 99%

Principal interacting orbital: A chemically intuitive method for deciphering bonding interaction

Zhang

Sheong

Lin

2020

WIREs Comput Mol Sci

100

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Modular bonding picture is a central part of chemical understanding as exemplified by the wide usage of Lewis structure as a chemical language to describe molecular electronic structures. A chemically intuitive bonding picture requires the descriptors to be localized and transferable. Molecular orbitals directly derived from quantum calculations are too delocalized to interpret in this regard, hence many efforts have been devoted to the development of bonding analysis methods. After a brief overview of various bonding analysis methods, this review outlines the framework of principal interacting orbital (PIO) analysis and presents its role in recovering intuitive chemical concepts and producing modular bonding pictures. The PIO analysis identifies the most important fragment orbitals that are involved in fragment interactions and characterizes a one-to-one orbital interaction pattern that underlies a unique set of bonding and anti-bonding orbitals derived from pairwise orbital interactions between two fragments. By making use of the principal component analysis (PCA), PIO analysis can effectively combine complex delocalized interaction patterns involved in numerous molecular orbitals into a handful of localized PIOs to provide easily interpretable results with intimate connection to localized chemical concepts, while maintaining necessary delocalized features when dealing with systems that involve mutlicentered interactions such as cluster compounds and various reactions. Such adaptability guarantees the robustness of PIO analysis with respect to change of substituents and the transferability of obtained PIOs across different systems. This article is categorized under: Structure and Mechanism > Molecular Structures K E Y W O R D S bonding theory, electronic structure, orbital interaction, principal interacting orbital 1 | INTRODUCTION Understanding chemical bonds and other chemical interactions is an elementary yet essential practice in chemistry and is fundamentally important when one tries to understand molecular geometric features and electronic properties. Long Jing-Xuan Zhang and Fu Kit Sheong contributed equally to this work. The code for PIO analysis is freely available at github.com/jxzhangcc/PIO.

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“…There are three great advantages of using this type of wave function to perform the interference energy analysis: (a) the atomic orbitals are uniquely defined within a given basis set (avoiding the arbitrariness involved in the choice of atomic orbitals); (b) the total interference energy and density per bond are automatically obtained; (c) contrary to Slater-type wave functions, GVB (and SCVB) wave functions are basis for the symmetric (or permutation) group as required by the permutation symmetry of the many-electrons Hamiltonian. The method has been applied to various classes of chemical species [51][52][53][54][55][56][57][58][59][60][61][62][63], diatomic and polyatomic molecules, with single, double and triple bonds, with different degrees of polarity, linear or branched, cyclic or not, conjugated and aromatics confirming that chemical bonds are formed due to the kinetic energy decrease caused by the quantum interference phenomenon taking place among the atomic orbitals involved in the bond, as predicted several decades ago by Ruedenberg [32]. The details of the method will not be presented but the interested reader may consult the appropriate literature [50,51].…”

Section: The Nature Of the Chemical Bond Quantum Interferencementioning

confidence: 99%

“…A detailed discussion of the (2c-1e) bonds can be found in Refs. [52,53] Molecules 2021, 26, x FOR PEER REVIEW 10 of 14 to the depth of the potential wells comes from the interference term, as in any other bond.…”

Section: The Nature Of the Chemical Bond Quantum Interferencementioning

confidence: 99%

“…A detailed discussion of the (2c-1e) bonds can be found in Refs. [52,53] Another interesting aspect revealed when chemical bonds are analyzed from the quantum mechanical interference perspective has to do with the usual classification of bonds as non-polar, covalent and ionic, again implying that different effects are responsible for the making of these bonds. The simplest and widely used criterion to predict the bond polarity is based on the difference of electronegativity (ΔXAB) of the two atoms making the bond.…”

Section: The Nature Of the Chemical Bond Quantum Interferencementioning

confidence: 99%

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The Valence-Bond (VB) Model and Its Intimate Relationship to the Symmetric or Permutation Group

Nascimento

2021

Molecules

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VB and molecular orbital (MO) models are normally distinguished by the fact the first looks at molecules as a collection of atoms held together by chemical bonds while the latter adopts the view that each molecule should be regarded as an independent entity built up of electrons and nuclei and characterized by its molecular structure. Nevertheless, there is a much more fundamental difference between these two models which is only revealed when the symmetries of the many-electron Hamiltonian are fully taken into account: while the VB and MO wave functions exhibit the point-group symmetry, whenever present in the many-electron Hamiltonian, only VB wave functions exhibit the permutation symmetry, which is always present in the many-electron Hamiltonian. Practically all the conflicts among the practitioners of the two models can be traced down to the lack of permutation symmetry in the MO wave functions. Moreover, when examined from the permutation group perspective, it becomes clear that the concepts introduced by Pauling to deal with molecules can be equally applied to the study of the atomic structure. In other words, as strange as it may sound, VB can be extended to the study of atoms and, therefore, is a much more general model than MO.

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One-electron bonds are not “half-bonds”

Cited by 23 publications

References 100 publications

Neither too Classic nor too Exotic: One‐Electron Na⋅B Bond in NaBH₃⁻ Cluster

Neither too Classic nor too Exotic: One‐Electron Na⋅B Bond in NaBH₃⁻ Cluster

Principal interacting orbital: A chemically intuitive method for deciphering bonding interaction

The Valence-Bond (VB) Model and Its Intimate Relationship to the Symmetric or Permutation Group

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One-electron bonds are not “half-bonds”

Cited by 23 publications

References 100 publications

Neither too Classic nor too Exotic: One‐Electron Na⋅B Bond in NaBH3− Cluster

Neither too Classic nor too Exotic: One‐Electron Na⋅B Bond in NaBH3− Cluster

Principal interacting orbital: A chemically intuitive method for deciphering bonding interaction

The Valence-Bond (VB) Model and Its Intimate Relationship to the Symmetric or Permutation Group

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Product

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Neither too Classic nor too Exotic: One‐Electron Na⋅B Bond in NaBH₃⁻ Cluster

Neither too Classic nor too Exotic: One‐Electron Na⋅B Bond in NaBH₃⁻ Cluster