Charges and bond orders in covalent xenon compounds using the structure—resonance paradigm

Herndon, William C.

doi:10.1016/0166-1280(88)80272-0

Cited by 4 publications

(3 citation statements)

References 80 publications

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“…However, it is implied whenever reference is made to the MO formulation of (4e,3c) bonding, and in ref because of the presence of (pseudo) one-electron bonds in some of the VB structures. Herndon has used increased-valence structures to describe the bonding for XeF 2 , XeF 4 , XeOF 4 , and XeF 6 , and therefore, singlet diradical structures contribute to the equivalent Lewis structure resonance scheme. We redescribe here aspects of the MO formulation of (4e,3c) bonding.…”

Section: (4e3c) Mo Configuration Singlet Diradical and Increased-vale...mentioning

confidence: 99%

Recoupled-Pair Bonding and 4-Electron 3-Center Bonding Units

Harcourt

2011

J. Phys. Chem. A

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Consideration is given to recoupled-pair bonding and the origin of electronic hypervalence for formulations of the bonding for symmetric 4-electron 3-center ((4e,3c)) bonding units with one overlapping atomic orbital per atomic center. Molecular orbital and valence bond theory for symmetric (4e,3c) bonding units is redescribed and applied to aspects of the bonding for SF(6) and CLi(6). The results of minimal basis set calculations for CLi(6) provide support for a hypothesis that two Li-C-Li (3e,3c) bonding units rather than two (4e,3c) bonding units are preferred for this molecule. Brief comments are also made on the use of [Formula: see text] and [Formula: see text] as valence bond structures for the three electron bond.

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Section: (4e3c) Mo Configuration Singlet Diradical and Increased-vale...mentioning

confidence: 99%

Recoupled-Pair Bonding and 4-Electron 3-Center Bonding Units

Harcourt

2011

J. Phys. Chem. A

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“…To be complete in the review of previous approaches, we should also mention an application of exchange perturbation theory by L. Jansen et al, which has probably only historical interest as well as a study of XeF 6 in terms of the structure- resonance paradigm by Herndon . Gutsev and Boldyrev have used X α calculations to interpret the photoelectron spectra of XeF 6 .…”

Section: Models Of Bonding In Xef6 and Isoelectronic Systemsmentioning

confidence: 99%

“…To be complete in the review of previous approaches, we should also mention an application of exchange perturbation theory by L. Jansen et al, 53 resonance paradigm by Herndon. 54 Gutsev and Boldyrev have used X R calculations to interpret the photoelectron spectra of XeF 6 . 55 Calculations by Malli et al including electron correlation and relativistic effects have been published for XeF 2 and XeF 4 56 and have been announced for XeF 6 57 but only for a regular octahedron.…”

Section: Models Of Bonding In Xef 6 and Isoelectronic Systemsmentioning

confidence: 99%

The Structure of XeF₆ and of Compounds Isoelectronic with It. A Challenge to Computational Chemistry and to the Qualitative Theory of the Chemical Bond

et al. 1996

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The preference of XeF6 for either a trigonally distorted or a regular octahedral structure is determined by a delicate balance of several competing factors. A regular octahedron is favored (a) by electron correlation and (b) by the relativistic contraction of the Xe 5s orbital. In contrast, higher angular momentum (in particular f-type) basis functions on Xe favor a distortion. While earlier SCF or other nonrelativistic calculations were in apparent agreement with experimental evidence for a distorted structure, this has been due to a partial cancellation of errors. The present study contains all-electron calculations as well as calculations of the valence-electrons in an effective core potential. For the former, electron correlation has been included at the MP2 level and relativistic effects by means of direct perturbation theory, for the latter the highest level was CCSD(T) for the treatment of electron correlation, and relativistic effects were simulated by means of a quasirelativistic effective core potential. Both sets of calculations lead to consistent results. These indicate that the “XeF6-like” XF6 compounds with light central atoms or ions like ClF6 - or BrF6 - prefer the structure of a regular octahedron. The same is true for KrF6, which is not stable with respect to Kr + 3F2 but probably represents a local minimum. For these light central atoms, electron correlation is decisive for a regular structure, while at Hartree−Fock level, i.e., ignoring correlation effects, the structure of lowest energy is distorted. Regular octahedra are also predicted for systems with very heavy central atoms like RnF6, AtF6 -, and PoF6 2-. For these compounds relativistic effects (supported by electron correlation) stabilize the regular octahedron. The situation is more complicated for XeF6, IF6 -, and TeF6 2-. Here the strong distortion found at nonrelativistic SCF level is compensated partly, but apparently not completely, by electron correlation and relativistic effects. This results in distorted, fluctuating structures with only little stabilization compared to the regular octahedron. A similar situation holds for SeF6 2-. None of the available simple models of main-group structural chemistry is able to predict or rationalize all of these structures. One inevitably has to use more subtle descriptions.

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Structure-resonance calculation of the ionization potential of saturated hydrocarbons

Srinivas

Radhakrishnan

1991

Journal of Molecular Structure

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Charges and bond orders in covalent xenon compounds using the structure—resonance paradigm

Cited by 4 publications

References 80 publications

Recoupled-Pair Bonding and 4-Electron 3-Center Bonding Units

Recoupled-Pair Bonding and 4-Electron 3-Center Bonding Units

The Structure of XeF₆ and of Compounds Isoelectronic with It. A Challenge to Computational Chemistry and to the Qualitative Theory of the Chemical Bond

Structure-resonance calculation of the ionization potential of saturated hydrocarbons

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Charges and bond orders in covalent xenon compounds using the structure—resonance paradigm

Cited by 4 publications

References 80 publications

Recoupled-Pair Bonding and 4-Electron 3-Center Bonding Units

Recoupled-Pair Bonding and 4-Electron 3-Center Bonding Units

The Structure of XeF6 and of Compounds Isoelectronic with It. A Challenge to Computational Chemistry and to the Qualitative Theory of the Chemical Bond

Structure-resonance calculation of the ionization potential of saturated hydrocarbons

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Product

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The Structure of XeF₆ and of Compounds Isoelectronic with It. A Challenge to Computational Chemistry and to the Qualitative Theory of the Chemical Bond