Quasi-Atomic Bonding Analysis of Xe-Containing Compounds

Heredia, Juan J. Duchimaza; Ruedenberg, Klaus; Gordon, Mark S.

doi:10.1021/acs.jpca.8b00115

Cited by 21 publications

(17 citation statements)

References 52 publications

(106 reference statements)

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“…By contrast, recent work by Ruedenberg and co-workers 11 – 16 indicates that the KE-lowering is critical in all bonds. This qualitative difference is not because of any error on their part or ours.…”

Section: Discussionmentioning

confidence: 80%

“…For the last nearly 60 years, this KElowering paradigm has been used to explain the quantum origin of covalent bonds via extrapolation from H þ 2 and H 2 [5][6][7][8][9][10][11][12] . Recently, work has been done to define a schema to allow this theory to be tested with other molecules [11][12][13][14][15][16] . However, the very strong assumption that the results for hydrogen are universal to other covalent bonds deserves scrutiny by alternative approaches.…”

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confidence: 99%

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Clarifying the quantum mechanical origin of the covalent chemical bond

Levine

Head‐Gordon

2020

Nat Commun

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Lowering of the electron kinetic energy (KE) upon initial encounter of radical fragments has long been cited as the primary origin of the covalent chemical bond based on Ruedenberg’s pioneering analysis of H$${}_{2}^{+}$$ 2 + and H2 and presumed generalization to other bonds. This work reports KE changes during the initial encounter corresponding to bond formation for a range of different bonds; the results demand a re-evaluation of the role of the KE. Bonds between heavier elements, such as H3C–CH3, F–F, H3C–OH, H3C–SiH3, and F–SiF3 behave in the opposite way to H$${}_{2}^{+}$$ 2 + and H2, with KE often increasing on bringing radical fragments together (though the total energy change is substantially stabilizing). The origin of this difference is Pauli repulsion between the electrons forming the bond and core electrons. These results highlight the fundamental role of constructive quantum interference (or resonance) as the origin of chemical bonding. Differences between the interfering states distinguish one type of bond from another.

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Section: Discussionmentioning

confidence: 80%

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confidence: 99%

Clarifying the quantum mechanical origin of the covalent chemical bond

Levine

Head‐Gordon

2020

Nat Commun

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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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“…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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Quasi-Atomic Bonding Analysis of Xe-Containing Compounds

Cited by 21 publications

References 52 publications

Clarifying the quantum mechanical origin of the covalent chemical bond

Clarifying the quantum mechanical origin of the covalent chemical bond

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

The Basics of Covalent Bonding in Terms of Energy and Dynamics

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