The Nature of the Chemical Bond from a Quantum Mechanical Interference Perspective

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

doi:10.1002/slct.201601535

Cited by 21 publications

(21 citation statements)

References 157 publications

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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%

“…According to the ∆X AB criterion, the HF molecule should be the most polar and BH the less polar bond among the AH molecules, in disagreement with the experimental dipole moments. Moreover, the bond in HF and LiF should be considered "ionic" (H + F − and Li + F − ) [54][55][56][57][58][59][60][61][62][63][64]. In addition, this criterion furnishes wrong predictions not only of relative magnitudes of dipole moments but also of their signs.…”

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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Section: The Nature Of the Chemical Bond Quantum Interferencementioning

confidence: 99%

Section: The Nature Of the Chemical Bond Quantum Interferencementioning

confidence: 99%

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

Nascimento

2021

Molecules

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“…8 This powerful method enables to partition the total electronic density and energy into physically well-grounded and straightforwardly interpretable parts. The method has been applied to various classes of chemical species, 9 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 10 in his seminal paper "The Physical Nature of the Chemical Bond". Ruedenberg's original method for the analysis of a chemical bond required choosing, by some criteria, a set of atomic orbitals among which the interference effect was to be evaluated.…”

Section: ■ Introductionmentioning

confidence: 93%

Substituent Effects on the Quantum Interference of Two-Center One-Electron Bonds: [B₂X₆]⁻ (X = H, F, Cl, CN, OH, CH₃, and OCH₃)

Sousa

Nascimento

2021

J. Phys. Chem. A

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The interference energy analysis (IEA) provided by the generalized product function energy partitioning (GPF-EP) method was applied to investigate the influence of the neighboring atoms on the nature of the two-center one-electron (2c1e) bonds in the anion dimers of BX3 species (X = H, F, Cl, CN, OH, CH3, and OCH3). The species were studied at the GVB-PP(6/12).SC(1,2)/6-31**G++ level of calculation. The IEA has revealed that there is a balance between two main factors determining the chemical stability of the species. Quantum interference acts as the sole stabilizing effect in the formation of the chemical bonds, particularly as the result of the drop in kinetic energy, and the electronegativity of the substituent has a direct influence on the magnitude of this effect. The quasi-classical energy is responsible for the destabilizing factors, mainly the group bulkiness, and the “electron-withdrawing” effect in the case of the cyano group.

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“…[4] Be that as it may, the deep roots of chemical bonding theory are still a source of bitter disputes among different schools. Some of them focus on the role of quantum mechanical interference, [5] others on the buildup of electron density in internuclear regions, [6] or on the decrease in the kinetic energy density accompanying bond formation, [7] to cite just a few. Although every chemist learns soon about Born's [8] statistical interpretation of quantum mechanics, and the cloud image of the square of an orbital as a probability density has become ubiquitous, it is surprising that not much effort has been devoted to understand the chemical bond in statistical (or probabilistic) terms.…”

Section: Introductionmentioning

confidence: 99%

Chemical Bonding from the Statistics of the Electron Distribution

Pendás

Francisco

2019

ChemPhysChem

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An introduction to the theory of chemical bonding from the point of view of the statistics of the electron distribution is presented. When atoms bind to form a molecule, their originally fixed number of electrons ceases to be a well‐defined observable, and this implies that their in‐the‐molecule electron populations fluctuate. If a chemically meaningful definition of an atom in a molecule is assumed, the probabilities of finding a given number of electrons in each of the atoms comprising the molecule can be computed. We show in this review how the complete electron distribution function (EDF) can be used to reconstruct the basic concepts and quantities used in chemical bonding without recourse to the orbital paradigm. From the statistical point of view, which inherits Born's probabilistic interpretation of quantum mechanics, a set of atoms are bonded when their electron populations are mutually dependent. We quantify this statistical dependence by the cumulant moments of the EDF, which provide a consistent description of both two‐ and multi‐center bonding. Particular attention is paid to building EDFs from model wavefunctions. With this, a simple bridge with orbital thinking is built. The statistical interpretation allows to easily classify all possible bonds of a given kind. We show that there are vast unexplored territories that should receive due consideration. Although building EDFs from models is easy and very instructive, the contrary is considerably more difficult. Recipes to extract chemical information from computed EDFs are also reviewed and, in all the cases, simple toy systems are used to show how the methodology works, allowing non‐experts to follow easily the presentation.

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The Nature of the Chemical Bond from a Quantum Mechanical Interference Perspective

Cited by 21 publications

References 157 publications

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

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

Substituent Effects on the Quantum Interference of Two-Center One-Electron Bonds: [B₂X₆]⁻ (X = H, F, Cl, CN, OH, CH₃, and OCH₃)

Chemical Bonding from the Statistics of the Electron Distribution

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The Nature of the Chemical Bond from a Quantum Mechanical Interference Perspective

Cited by 21 publications

References 157 publications

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

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

Substituent Effects on the Quantum Interference of Two-Center One-Electron Bonds: [B2X6]− (X = H, F, Cl, CN, OH, CH3, and OCH3)

Chemical Bonding from the Statistics of the Electron Distribution

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Substituent Effects on the Quantum Interference of Two-Center One-Electron Bonds: [B₂X₆]⁻ (X = H, F, Cl, CN, OH, CH₃, and OCH₃)