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

Lindquist, Beth A.; Dunning, Thom H.

doi:10.1007/s00214-013-1443-8

Cited by 16 publications

(11 citation statements)

References 55 publications

(72 reference statements)

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“…As has been shown by Dunning and co-workers, the structures and energetics of all of the hypervalent molecules that they studiedSF n , 137 SF n-1 Cl, 143 SCl n , 144 PF n , 145 PF n-1 Cl, 146 H(SO), 147 S 2 F 4 , 148,149 SO 2 , 150,151 Cl n SO, 152 ClF n , 153 ClF n + , 154 and ClF n −155 follow the pattern observed above for SF n (see also refs 156, 157, and 158). In all of these molecules there are polar covalent bonds, recoupled pair bonds, and recoupled pair bond dyads with the most stable structures and the bond energies being determined by the interplay of these three types of bonding.…”

Section: Insights Into the Electronic Structure Ofmentioning

confidence: 81%

Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds

Dunning

Cooper

et al. 2021

J. Phys. Chem. A

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Spin-Coupled Generalized Valence Bond (SCGVB) theory provides the foundation for a comprehensive theory of the electronic structure of molecules. SCGVB theory offers a compelling orbital description of the electronic structure of molecules as well as an efficient and effective zero-order wave function for calculations striving for quantitative predictions of molecular structures, energetics and other properties. The orbitals in the SCGVB wave function are usually semi-localized and, for most molecules, can be interpreted using concepts familiar to all chemists (hybrid orbitals, localized bond pair, lone pairs, etc.). SCGVB theory also provides new perspectives on the nature of the bonds in molecules such as C2, Be2 and SF4/SF6. SCGVB theory contributes unparalleled insights into the underlying cause of the first-row anomaly in inorganic chemistry as well as the electronic structure of organic molecules and the electronic mechanisms of organic reactions. The SCGVB wave function accounts for nondynamical correlation effects and, thus, corrects the most serious deficiency in molecular orbital (RHF) wave functions. Dynamical correlation effects, which are critical for quantitative predictions, can be taken into account using the SCGVB wave function as the zero-order wave function for multireference configuration interaction or coupled cluster calculations.* In prior articles in the literature the Spin-Coupled Generalized Valence Bond wave function has usually been referred to as the Spin-Coupled Valence Bond (SCVB) wave function or the full Generalized Valence Bond (full GVB) wave function. These wave functions are identical; to prevent confusion, the authors have adopted the allencompassing SCGVB name. Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds3 and recoupled pair bond dyad. 36 The SCGVB wave function describes molecules in terms of orbitals that are optimized at each geometry, allowing the atomic orbitals to change as a result of molecule formation. In addition to the changes in the orbitals, optimization of the general spin function used in the SCGVB wave function allows the spin function to change from that appropriate for the separated atoms or fragments to that appropriate for the molecule. SCGVB theory addresses a major limitation of RHF theory, providing an excellent zero-order description of molecules that require multiconfiguration descriptions, the making/breaking of bonds, and many chemical reactions and excited states. For most molecules, the SCGVB wave function captures the essential features of the FORS/CASSCF wave functions, with much reduced complexity compared to these latter wave functions.

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Section: Insights Into the Electronic Structure Ofmentioning

confidence: 81%

Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds

Dunning

Cooper

et al. 2021

J. Phys. Chem. A

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“…14 We have also found that recoupled pair bonds and recoupled pair bond dyads are important in the oxides and hydroxides of the second row, late p-block elements. 15,16 With divalent ligands, such as oxygen, it is possible to form recoupled pair bonds in the π systems of molecules as well as in the σ systems. 15,16 In these earlier studies, it was noted that the early pblock elements also form recoupled pair bonds, a fact that was recognized much earlier by Goddard and coworkers, 17,18 but without a specific label for the bond type or an appreciation for the role of this type of bond in hypervalent (or hypercoordinated) compounds of the late p-block elements.…”

Section: Introductionmentioning

confidence: 99%

“…15,16 With divalent ligands, such as oxygen, it is possible to form recoupled pair bonds in the π systems of molecules as well as in the σ systems. 15,16 In these earlier studies, it was noted that the early pblock elements also form recoupled pair bonds, a fact that was recognized much earlier by Goddard and coworkers, 17,18 but without a specific label for the bond type or an appreciation for the role of this type of bond in hypervalent (or hypercoordinated) compounds of the late p-block elements. In fact, the carbon atom, with a ground state valence electron configuration of 2s 2 2p x 1 2p z 1 , could rightfully be considered hypervalent (or hypercoordinated) in CH 4 and CF 4 .…”

Section: Introductionmentioning

confidence: 99%

Fundamental aspects of recoupled pair bonds. I. Recoupled pair bonds in carbon and sulfur monofluoride

Dunning

Takeshita

2015

The Journal of Chemical Physics

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The number of singly occupied orbitals in the ground-state atomic configuration of an element defines its nominal valence. For carbon and sulfur, with two singly occupied orbitals in their 3P ground states, the nominal valence is two. However, in both cases, it is possible to form more bonds than indicated by the nominal valence—up to four bonds for carbon and six bonds for sulfur. In carbon, the electrons in the 2s lone pair can participate in bonding, and in sulfur the electrons in both the 3p and 3s lone pairs can participate. Carbon 2s and sulfur 3p recoupled pair bonds are the basis for the tetravalence of carbon and sulfur, and 3s recoupled pair bonds enable sulfur to be hexavalent. In this paper, we report generalized valence bond as well as more accurate calculations on the a4Σ− states of CF and SF, which are archetypal examples of molecules that possess recoupled pair bonds. These calculations provide insights into the fundamental nature of recoupled pair bonds and illustrate the key differences between recoupled pair bonds formed with the 2s lone pair of carbon, as a representative of the early p-block elements, and recoupled pair bonds formed with the 3p lone pair of sulfur, as a representative of the late p-block elements.

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“…We note that the charge transfer is lowest (−0.07 e − ) when only one S is bound to the Pt surface, followed by the tri-bound 4F S,O_A (−0.21 e − ) and the tetra-bound 4F S,O_A (−0.41 e − ) configurations. When comparing the S-O bond length, it can be seen that the adsorption configuration can cause a deviation of up to 0.2 Å from the experimentally measured S-O bond length of 1.44 Å[81], which correlates with the 4F S-bound structure.This shows that the bond lengths and charge transfer are dependent on the bond order and type of bonds formed during adsorption [82]. On the Pt (011) surface four stable adsorption configurations were observed, one being S-bound and three S,O-bound.…”

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confidence: 71%

Behavior of S, SO, and SO3 on Pt (001), (011), and (111) surfaces: A DFT study

Ungerer

Sittert

Leeuw

2021

The Journal of Chemical Physics

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In the hybrid sulphur (HyS) cycle, the reaction between SO 2 and H 2 O is manipulated to produce hydrogen, with water and sulphuric acid as by-products. However, sulphur poisoning of the catalyst has been widely reported to occur in this cycle, which is due to strong chemisorption of sulphur on the metal surface. The catalysts may deactivate as a result of these impurities present in the reactants or incorporated in the catalyst during its preparation and operation of the HyS cycle.Here, we report a density functional theory (DFT) investigation of the interaction between S, SO and SO 3 with the Pt (001), ( 011) and ( 111) surfaces. First, we have investigated the adsorption of single gas phase molecules on the three Pt surfaces. During adsorption, the 4F hollow sites on the (001) and (011) surfaces and the fcc hollow site on the (111) surface were preferred. S adsorption followed the trend of (001) 4F > (011) 4F > (111) fcc , while SO adsorption showed (001) 4F > (011) bridge/4F > (111) fcc and SO 3 adsorption was most stable in a S,O,O bound configuration on the (001) 4F > (011) 4F > (111) fcc sites.The surface coverage was increased on all the surfaces until a monolayer was obtained. The highest surface coverage for S shows the trend (001) S = (111) S > (011) S , and for SO it is (001) SO > (011) SO > (111) SO , similar to SO 3 where we found (001) SO3 > (011) SO3 > (111) SO3 . These trends indicate that the (001) surface is more susceptible to S species poisoning. It was also evident that both the (001) and (111) surfaces were reactive towards S, leading to the formation of S 2 . High coverage of SO 3 showed the formation of SO 2 and SO 4 , especially on the (011) surface. The thermodynamics indicated that an increased temperature up to 2000 K resulted in Pt surfaces fully covered with elemental S. The SO coverage showed θ ≥ 1.00 on both the (001) and (011) surfaces, and θ = 0.78 for the (111) in the experimental region where the HyS cycle is operated. Lower coverages of SO 3 were observed due to the size of the molecule.

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

Cited by 16 publications

References 55 publications

Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds

Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds

Fundamental aspects of recoupled pair bonds. I. Recoupled pair bonds in carbon and sulfur monofluoride

Behavior of S, SO, and SO3 on Pt (001), (011), and (111) surfaces: A DFT study

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