Bond orders and valences in some simple sulphur compounds

Mayer, I.; Révész, M.

doi:10.1016/s0020-1693(00)82616-x

Cited by 33 publications

(8 citation statements)

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“…(2) In the general case one obtains numbers which are not strictly integers, but even for larger molecules are close to the corresponding classical values. (3) The deviations from the integer values are due to the bond polarity and delocalization effects, so often can be well interpreted in simple physical terms.…”

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confidence: 77%

Bond orders and valences from ab initio wave functions

Mayer

1986

Int J of Quantum Chemistry

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The definition and properties of the bond order and valence indices calculated from ab initio wave functions are summarized. Their physical interpretation, relationships to the exchange effects in bonding and generalization to correlated wave functions are also discussed. Some examples with typical bond order and valence values are shown. I. The DefinitionsThe present communication deals with the concept of the bond order (multiplicity) and valence indices calculated from the ab initio wave functions of different molecules [l-81. These are parameters of direct chemical significance, because they can be put well into correspondence with the corresponding classical chemical notions. They may be useful both in studying the links between quantum mechanics and "ordinary" chemistry in general and in giving better interpretations and deeper understanding of the results of the actual quantum chemical calculations for particular systems. Bond order between atoms E ( B # A )

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confidence: 77%

Bond orders and valences from ab initio wave functions

Mayer

1986

Int J of Quantum Chemistry

Self Cite

451

240

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“…In their experiments, a planar cis -OSSO chain of C 2 v symmetry with two double S–O bonds and a central S–S bond with partial double bond character was identified by microwave spectroscopy. Subsequent theoretical and experimental studies ,− confirmed this structure and showed the existence of other isomers of S 2 O 2 . The SCF+MPn (self-consistent-field + Møller–Plesset) calculations of Marsden and Smith predicted a planar trigonal form of C 2 v symmetry, resembling that of the SO 3 molecule, being the most stable one (of singlet multiplicity) and therefore lower in energy than the cis -OSSO isomer observed by Lovas et al They also found a trans structure ( trans -OSSO) and a cyclic form with energies very close to that of the corresponding cis form and several other isomers at higher energies.…”

Section: Introductionmentioning

confidence: 80%

S₂O₂^q+ (q = 0, 1, and 2) Molecular Systems: Characterization and Atmospheric Planetary Implications

et al. 2021

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We use accurate ab initio methodologies at the coupled cluster level ((R)CCSD(T)) and its explicitly correlated version ((R)CCSD(T)-F12) to investigate the electronic structure, relative stability, and spectroscopy of the stable isomers of the [S2O2] system and of some of its cations and dications, with a special focus on the most relevant isomers that could be involved in terrestrial and planetary atmospheres. This work identifies several stable isomers (10 neutral, 8 cationic, and 5 dicationic), including trigonal-OSSO, cis-OSSO, and cyc-OSSO. For all these isomers, we calculated geometric parameters, fragmentation energies, and simple and double ionization energies of the neutral species. Several structures are identified for the first time, especially for the ionic species. Computations show that in addition to cis-OSSO and trans-OSSO proposed for the absorption in the near-UV spectrum of the Venusian atmosphere other S2O2, S2O2 +, and S2O2 2+ species may contribute. Moreover, the characterization of the stability of singly and doubly charged S2O2 entities can also be used for their identification by mass spectrometry and UV spectroscopy in the laboratory or in planetary atmospheres. In sum, the quest for the main UV absorber in Venus’ atmosphere is not over, since the physical chemistry of sulfur oxides in Venus’ atmosphere is far from being understood.

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“…It was suggested that the doubly occupied O2p lone pair orbitals back-bond to the S3d orbitals of the central atom [5,6]. However, detailed calculations of various hypervalent molecules show that S3d functions only provide polarization and correlation effects [7][8][9]; these functions do not participate as 3d valence orbitals in the bonding in the sulfinyls.…”

Section: Introductionmentioning

confidence: 99%

The nature of the SO bond of chlorinated sulfur–oxygen compounds

Lindquist

Dunning

2014

Theor Chem Acc

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Sulfur-oxygen chemistry encompasses a rich variety of chemical species and reactions. Sulfur-oxygen bonds can be quite short and strong, and historically, there has been disagreement as to the nature of the SO bond in sulfinyl groups. Early work invoked participation by the 3d orbitals of sulfur to explain the apparent double-bond character of sulfinyl bonds, but modern calculations have clearly established that sulfur 3d atomic orbitals do not participate as valence orbitals in hypervalent sulfur compounds. In prior work, we used generalized valence bond (GVB) theory to explain the features of the SO bond in the HSO/SOH structural isomers, and we extend that work here to the chlorinated analogs (ClSO/SOCl). We also use GVB theory to elucidate the nature of the bonding in Cl 2 SO and its higher energy structural isomer ClSOCl. We find that recoupled pair bonding, which we first introduced in our study of sulfur fluorides, is integral to describing the SO bond in all of these species. We also connect our analysis to the use of hyperconjugation to explain the backbonding in the p system in the sulfinyl halides.

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Bond orders and valences in some simple sulphur compounds

Cited by 33 publications

References 10 publications

Bond orders and valences from ab initio wave functions

Bond orders and valences from ab initio wave functions

S₂O₂^q+ (q = 0, 1, and 2) Molecular Systems: Characterization and Atmospheric Planetary Implications

The nature of the SO bond of chlorinated sulfur–oxygen compounds

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Bond orders and valences in some simple sulphur compounds

Cited by 33 publications

References 10 publications

Bond orders and valences from ab initio wave functions

Bond orders and valences from ab initio wave functions

S2O2q+ (q = 0, 1, and 2) Molecular Systems: Characterization and Atmospheric Planetary Implications

The nature of the SO bond of chlorinated sulfur–oxygen compounds

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Product

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S₂O₂^q+ (q = 0, 1, and 2) Molecular Systems: Characterization and Atmospheric Planetary Implications