Hypervalent molecules sulfurane (SH4) and persulfurane (SH6)

Schwenzer, Gretchen M.; Schaefer, Henry F.

doi:10.1021/ja00839a019

Cited by 43 publications

(12 citation statements)

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“…The orbital energies of the occupied and low-lying Rydberg and S-H antibonding ~* virtual orbitals are given in table 1. The orbital ordering is that found in previous calculations [8][9][10][11][12][13]17], although the set of low-lying Rydberg orbitals which occur in the present calculations have no analogue in treatments with conventional basis sets. (a) Ground state is lal z 2al z lb2 ~ 3al ~ lbt ~ 4al 2 2b22 5at 2 2bl 2.…”

Section: Scf Calculations On the Ground Statesupporting

confidence: 60%

“…The latter result is 0-0051 hartree above that of Schwenzer and Schaefer [11] and 0-0318 hartree above the estimated Hartree-Fock limit [13]. The orbital energies of the occupied and low-lying Rydberg and S-H antibonding ~* virtual orbitals are given in table 1.…”

Section: Scf Calculations On the Ground Statementioning

confidence: 75%

“…Experimentally its ultra-violet [1,2] and X-ray [3] photoelectron spectra have been measured, as has the Kfl emission and K-absorption spectra [4][5][6] and the 2p-excitation spectrum in the XUV region [7]. In common with previous theoretical studies of H2S conducted at the SCF level [8][9][10][11], recent valence bond [12] and coupled electron pair (CEPA) and pair natural orbital configuration interaction (PNO-CI) [13] studies have been mainly confined to the ground state of the neutral molecule. Studies of the low-lying excited states have in general relied on less sophisticated calculations [14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 91%

“…8 of reference [26] used throughout. The s basis set used for hydrogen was Dunning's [27] (4s/2s) contraction of Huzinaga's [28] primitive gaussian basis, with the optimized hydrogen scale factor of 1"19 due to Schwenzer and Schaefer [11]. The resulting [6s4p/2s] is of double-zeta quality (DZ basis).…”

Section: Scf Calculations On the Ground Statementioning

confidence: 99%

“…Using a more flexible [7sSp/3s] contraction Schwenzer and Schaefer found the SCF ground-state optimized geometry to be in surprisingly poor agreement with experiment, with the bond distance too long by 0.029 A and bond angle too large by 4 ~ , and attributed this discrepancy to the absence of polarization functions. Thus the DZ basis was augmented by a set of d functions on sulphur and a set of hydrogenic p functions with optimized exponents of 0.846 and 0.595 respectively taken from reference [11]. The total SCF energy from the resulting [6s4pld/2slp] basis set (DZP basis) was -398.6869 hartree, in close agreement with the value obtained by Rothenberg et al [8] (-398.6862 hartree) using the same number of contracted functions t. An investigation of the ground-state geometry using the DZP basis will be discussed in w…”

Section: Scf Calculations On the Ground Statementioning

confidence: 99%

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Ab initio study of the ground and excited states of hydrogen sulphide using SCF and CI calculations

Guest

Rodwell

1976

Molecular Physics

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Results from ab initio SCF and CI calculations on the ground state and low-lying valence and Rydberg states of H2S are reported. A double ~ basis of contracted gaussian functions augmented by polarization and diffuse 3d, 4s and 4p functions is used for the calculations. The geometries of various excited states are studied by means of SCF calculations. The first observed band in the absorption spectrum is predicted to arise from the overlapping of transitions from the 2bl orbital to a Rydberg 4s and strongly bent valence upper state. The calculations support the assignment of other spectral features to transitions from the 2bl to components of the Rydberg 3d and 4p orbitals.

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Section: Scf Calculations On the Ground Statesupporting

confidence: 60%

Section: Scf Calculations On the Ground Statementioning

confidence: 75%

Section: Introductionmentioning

confidence: 91%

Section: Scf Calculations On the Ground Statementioning

confidence: 99%

Section: Scf Calculations On the Ground Statementioning

confidence: 99%

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Ab initio study of the ground and excited states of hydrogen sulphide using SCF and CI calculations

Guest

Rodwell

1976

Molecular Physics

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Die chemische Bindung bei den höheren Hauptgruppenelementen

1984

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Viele qualitative Konzepte zur Beschreibung der chemischen Bindung, die aus der Frühzeit der Theoretischen Chemie stammen, sind zwar durch quantenchemische Rechnungen an Molekülen mit Atomen von Elementen der zweiten Periode (Li bis Ne) gestützt worden, lassen sich aber – entgegen einer weit verbreiteten Auffassung – nicht ohne weiteres auf Moleküle mit Atomen von Elementen der höheren Perioden verallgemeinern. Insbesondere ist der Begriff der Hybridisierung bei den Atomen aus höheren Perioden nur mit Vorsicht zu verwenden. Der wesentliche Unterschied zwischen den Atomen aus der zweiten und denen aus höheren Perioden besteht darin, daß bei den einen die Rümpfe nur s‐AOs, bei den letztgenannten aber zumindest s‐ und p‐AOs enthalten. Das hat zur Folge, daß die s‐ und p‐Valenz‐AOs der Atome aus der zweiten Periode ungefähr im gleichen räumlichen Bereich lokalisiert sind, während sich bei den Atomen aus den höheren Perioden die p‐Valenz‐AOs deutlich weiter außen befinden. Hierauf beruht die größere Bedeutung der „lone‐pair‐Abstoßung”︁ und der „isovalenten Hybridisierung”︁ sowie schließlich die Schwäche von Einfachbindungen und die Stärke von Mehrfachbindungen bei den leichten Hauptgruppenelementen. Die Valenzausweitung (Verletzung der Oktettregel) bei Verbindungen der höheren Hauptgruppenelemente hängt nur sehr wenig mit der Verfügbarkeit von d‐AOs zusammen, mehr mit der Größe dieser Atome und somit der geringeren gegenseitigen sterischen Hinderung von Liganden, etwas auch mit der geringeren Elektronegativität der schweren Atome. Jedenfalls kommt das Modell von Elektronenüberschuß‐Mehrzentrenbindungen der Realität näher als dasjenige von Hybriden unter d‐AO‐Beteiligung. Die XO‐Bindungen in Phosphanoxiden, Sulfoxiden, Oxosäuren und verwandten Verbindungen werden besser semipolar als als echte Doppelbindungen formuliert, auch wenn viele Eigenschaften die andere Vorstellung nahelegen. – Das zunehmende Interesse der Theorie an den Verbindungen der höheren Hauptgruppenelemente fällt zeitlich zusammen mit neuen und zum Teil spektakulären experimentellen Forschungsergebnissen aus der Chemie dieser Elemente.

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Chemical Bonding in Higher Main Group Elements

Kutzelnigg

1984

Angew. Chem. Int. Ed. Engl.

944

584

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Many concepts used for a qualitative description of chemical bonding that originated in the early days of theoretical chemistry have been vindicated recently by quantum chemical calculations, at least as far as first row elements are concerned. However, many concepts that have been justified for first row elements (Li to Ne) cannot-contrary to widespread belief-be generalized to the higher main group elements. This applies particularly to the concept of hybridization, which should be viewed with considerable caution. The essential difference between the atoms of the first and higher rows is that the cores of the former contain only s-AOs, whereas the cores of the latter include at least s-and p-AOs. As a consequence, the s and p valence AOs of first row atoms are localized in roughly the same region of space, while the p valence AOs of higher row atoms are much more extended in space. This has the consequence that for the light main group elements both lone-pair repulsion and isovalent hybridization play a greater role than for the heavy main group elements. Furthermore, this implies that single bonds between first row elements are weak and multiple bonds are strong, whereas for the second or higher row elements single bonds are strong and multiple bonds weak. The "extended valence" (violation of the octet rule) observed in compounds of higher main group elements has very little to do with the availability of d-AOs but is due rather to the size of these atoms and thus to the reduced steric hindrance between ligands and, to a lesser extent, also to the lower electronegativity of the heavy atoms. A model based on the concept of electron-rich multicenter bonds is certainly closer to reality than one involving hybrids with the participation of d-AOs. The XO bonds in phosphane oxides, sulfoxides, 0x0 acids and related compounds are better formulated as semipolar rather than as true double bonds, even if they behave in some respects like double bonds.-The growing interest of theorists in compounds of higher main group elements parallels new and, in some instances, spectacular results of experimental research on the chemistry of these elements.

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Hypervalent molecules sulfurane (SH4) and persulfurane (SH6)

Abstract: Pseudo-first-order kinetics were observed in ref 25. Making an approximation that the cytochrome oxidase concentration is at least 20-fold in excess of the ferrocytochrome c concentration, an estimated upper limit to the second-order rate constant is calculated as given. (29) K.

Cited by 43 publications

References 5 publications

Ab initio study of the ground and excited states of hydrogen sulphide using SCF and CI calculations

Ab initio study of the ground and excited states of hydrogen sulphide using SCF and CI calculations

Die chemische Bindung bei den höheren Hauptgruppenelementen

Chemical Bonding in Higher Main Group Elements

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