A Quasi-Atomic Analysis of Three-Center Two-Electron Zr–H–Si Interactions

Heredia, Juan J. Duchimaza; Sadow, Aaron D.; Gordon, Mark S.

doi:10.1021/acs.jpca.8b09530

Cited by 24 publications

(20 citation statements)

References 52 publications

(118 reference statements)

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“…The individual contributions of these QUAO pairs to the molecular interatomic kinetic energy lowering Δ T (inter) of eq have been found to be negative for all bonds (close to 100) in all examined molecules, ,− including rhodium boride. It can therefore be inferred that these individual contributions are the drivers for the formation of the individual bonds .…”

Section: Quasi-atomic Bonding Analysismentioning

confidence: 91%

Multiple Bonding in Rhodium Monoboride. Quasi-atomic Analyses of the Ground and Low-Lying Excited States

2021

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The bonding structures of the ground state and the lowest five excited states of rhodium monoboride are identified by determining the quasi-atomic orbitals in full valence space MCSCF wave functions and the interactions between these orbitals. A quadruple bond, namely two π-bonds and two σ-bonds, is identified and characterized for the X1Σ+ ground state, in agreement with a previous report ( Cheung Cheung J. Phys. Chem. Lett202011659663). However, in all excited states, the bonding is predicted to be weaker because, in these states, one of the σ-bonding interactions has a small magnitude. In the a3Δ and A1Δ states, the bond order is between a triple and quadruple bond. In the b3Σ+ state, the Rh–B linkage is a triple bond. In the c3Π and B1Π states, the atoms are linked by a double bond due to an additional weakening of the two π-bonds. The decreases in the predicted bond strengths are reflected in the decreases of the predicted binding energies and in the increases of the predicted bond lengths from the X1Σ+ ground state to the c3Π and the B1Π excited states. Notably, the 5pσ orbital of rhodium, which is vacant in the ground state of the atom, plays a significant role in the molecule.

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Section: Quasi-atomic Bonding Analysismentioning

confidence: 91%

Multiple Bonding in Rhodium Monoboride. Quasi-atomic Analyses of the Ground and Low-Lying Excited States

2021

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“…The original work left opened the question of the most appropriate choice of atomic-like orbitals on which to express the density and conduct such an analysis. However, later papers by Ruedenberg and co-workers discuss possible ways of constructing sets of such "quasi-atomic" orbitals and examined a variety of molecules and chemical bonds to consistently show the correctness of his predictions [37][38][39][40][41][42][43][44][45][46][47][48][49].…”

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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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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“…Of particular interest are the kinetic bond orders that provide computationally efficient energy-based quantitative estimates of covalent bonding. The method has been applied to a range of large systems, such as xenon containing molecules [98], the disilyl zirconocene amide cation [99], and cerium oxides [100].…”

Section: The Effects Of Interference On Charge Movement and Energiesmentioning

confidence: 99%

“…Indeed the earliest quantum mechanical computations, ab initio and semi-empirical, focused on questions of bonding, but gradually the balance shifted and nowadays the majority of quantum chemical calculations, performed typically on supercomputers, focus on modeling chemical processes, structure, and properties. Yet, as chemists we want to, indeed need to, understand bonding and considerable effort is directed to the extraction of simple-to-understand bonding information from complex wave functions that are often characterized by millions of numbers [90][91][92][93][94][95][96][97][98][99][100][101][102][103][104]. In contrast, this paper is concerned with the fundamental aspects of bonding, a problem of long standing, rather than the immediate interpretation of results from large scale quantum chemical calculations.…”

Section: Introductionmentioning

confidence: 99%

The Basics of Covalent Bonding in Terms of Energy and Dynamics

Nordholm

Bacskay

2020

Molecules

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We address the paradoxical fact that the concept of a covalent bond, a cornerstone of chemistry which is well resolved computationally by the methods of quantum chemistry, is still the subject of debate, disagreement, and ignorance with respect to its physical origin. Our aim here is to unify two seemingly different explanations: one in terms of energy, the other dynamics. We summarize the mechanistic bonding models and the debate over the last 100 years, with specific applications to the simplest molecules: H2+ and H2. In particular, we focus on the bonding analysis of Hellmann (1933) that was brought into modern form by Ruedenberg (from 1962 on). We and many others have helped verify the validity of the Hellmann–Ruedenberg proposal that a decrease in kinetic energy associated with interatomic delocalization of electron motion is the key to covalent bonding but contrary views, confusion or lack of understanding still abound. In order to resolve this impasse we show that quantum mechanics affords us a complementary dynamical perspective on the bonding mechanism, which agrees with that of Hellmann and Ruedenberg, while providing a direct and unifying view of atomic reactivity, molecule formation and the basic role of the kinetic energy, as well as the important but secondary role of electrostatics, in covalent bonding.

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A Quasi-Atomic Analysis of Three-Center Two-Electron Zr–H–Si Interactions

Cited by 24 publications

References 52 publications

Multiple Bonding in Rhodium Monoboride. Quasi-atomic Analyses of the Ground and Low-Lying Excited States

Multiple Bonding in Rhodium Monoboride. Quasi-atomic Analyses of the Ground and Low-Lying Excited States

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

The Basics of Covalent Bonding in Terms of Energy and Dynamics

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