Bonding or Nonbonding? Description or Explanation? “Confinement Bonding” of He@adamantane

Wang, Shuguang; Qiu, Ye; Schwarz, W. H. Eugen

doi:10.1002/chem.200802596

Cited by 33 publications

(16 citation statements)

References 113 publications

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“…The metastable molecular title compound has already been investigated several times. [1][2][3][4][5][6][7] Here, we will apply a quantum computational approach (nonrelativistic density functional theory (DFT) at the lowest-order Born-Oppenheimer (BO) approximation, and also some post-Hartree-Fock MP2 calculations) that reproduces the known (experimentally derived and computed) data reasonably well.…”

Section: Introductionmentioning

confidence: 87%

“…The trapping effect of the IC that outstrips the antibonding repulsions between the components has recently been discussed under the rubric of confinement. [5] In the case of the title compound, either strong destabilizing (MZB-EDA) or strong stabilizing (QTAiM-IQA) interactions were postulated between the components of the IC (noble gas atom He and saturated closed-shell adamantane cage). [2][3][4][5][6][7] Paradoxical bond descriptions are also well known for several other complexes.…”

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confidence: 99%

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Antibond Breaking—The Formation and Decomposition of He@Adamantane: Descriptions, Explanations, and Meaning of Concepts

Wang

Qiu

Schwarz

2010

Chemistry A European J

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The reaction path from the inclusion complex He@adamantane to its two separated fragments over the transition barrier is investigated by using quantum chemistry. The changes of structure and wavefunction are intuitively anticipated, accurately computed, and qualitatively rationalized. With the help of the traditional concepts of chemical bonding and nonbonding interactions, and with numerical results from a chemically oriented energy-partitioning approach, we can rationalize the details of the chemical process, and qualitatively predict and interpret the two chosen alternative descriptions: the energy-partitioning approach and the topological electron-density analysis. The meaning of bonding within these two approaches, and unsolved aspects of the latter tool are clarified.

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Section: Introductionmentioning

confidence: 87%

mentioning

confidence: 99%

Antibond Breaking—The Formation and Decomposition of He@Adamantane: Descriptions, Explanations, and Meaning of Concepts

Wang

Qiu

Schwarz

2010

Chemistry A European J

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“…[22], "explanations and interpretations in the complicated domain of chemistry are ambiguous. Various interpretations can all be logically consistent".…”

Section: Reminiscencesmentioning

confidence: 99%

“…in the framework of the harmonic approximation, and by formula (22), i.e. making allowance for the anharmonism, are quoted in Table 4.…”

Section: Esk Is Thankful Tomentioning

confidence: 99%

On the Problem of He–He Bond in the Endohedral Fullerene He2@C60

2018

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For more than twenty years, the endohedral fullerene cavity is attracting a permanent attention of experimenters and theorists, computational chemists and physicists, who apply their efforts to simulate encapsulated atoms and molecules in the fullerene cavity on computers and analyze the arising phenomena of atomic bonding. In this work, recent developments concerning the endohedral fullerene He2@C60, in particular, its experimental observation and relevant computational works, are reviewed. On the one hand, the dihelium He2 embedded into the C60 cavity is observed experimentally. On the other hand, the computer simulation shows that each of the He atoms is characterized by an insignificant charge transfer to C60, so that the He dimer exists as a partially charged (He + )2 entity. The key issue of the work concerns the existence of a bond between those two helium atoms. Since the bond is created between two particles, we assert that it suffices to define the bond on the basis of the molecular Löwdin's postulate and use it to study the He dimer in the C60 cavity in terms of the He-He potential energy well. It was analytically demonstrated that this well can contain at least one bound (ground) state. Therefore, according to Löwdin's postulate, which is naturally anticipated in quantum theory, the conclusion is drawn that the (He + )2 entity is a diatomic molecule, in which two heliums are bound with each other. On the basis of those arguments, the concept of endohedral fullerene stability is proposed to be extended. K e y w o r d s: fullerene, endohedral fullerene, He@C60, He2@C60, bond, molecule, Löwdin's postulate.

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“…They appear more or less accidentally and seem to have no specific meaning when they just show up at equilibrium bond lengths. Similarly, there may occur bond paths in the electron density distribution sometimes rather accidentally, indicating the near-formation of a bond, or just a non-bonded contact, looking from various chemical points of view [75,76].…”

Section: W H Eugen Schwarzmentioning

confidence: 99%