Microwave spectrum and molecular structure of thionyl chloride

Mata, Fernando; Carballo, Norberto

doi:10.1016/0022-2860(83)85016-9

Cited by 17 publications

(11 citation statements)

References 9 publications

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“…This compares well with the calculated structure of Cl 2 SO: R e (ClS) = 2.069 Å , \ClSCl = 95.5, R e (SO) = 1.435 Å , and \Cl 2 S-SO = 115.9 (the latter is the angle between the bisector of the Cl 2 S plane and the SO bond); see Table 2. These geometric parameters compare well with prior computational and experimental studies of Cl 2 SO [48][49][50][51]. Clearly, this approach provides a compelling description of the bonding in the Cl 2 SO molecule.…”

Section: The CL 2 So Isomersupporting

confidence: 71%

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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Section: The CL 2 So Isomersupporting

confidence: 71%

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

Lindquist

Dunning

2014

Theor Chem Acc

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“… Optimized geometries obtained at the a MP2(Full)/6-31G(d), b MP2/6-31G(d′), c B3LYP/6-31G(d), d B3LYP/6-311G(2d,d,p), e B3LYP/6-31G(2df,p), and f B3LYP/cc-pVTZ+d level of theory. g Reference . h Reference . i Reference . j Reference . k Reference . l Reference . m Reference . n Reference . o Reference . p Reference . q Reference . r Reference . s Excluded from the statistical analyses. t Reference . …”

Section: Resultsmentioning

confidence: 99%

Computational Tests of Quantum Chemical Models for Structures, Vibrational Frequencies, and Heats of Formation of Molecules with Phosphorus and Sulfur Atoms

2010

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The Gaussian-n, complete basis set, and Weizmann-1 quantum chemical models for heats of formation are applied to a set of molecules with relevance to the combustion or pyrolysis of chemical warfare materials. Most of these models generate standard deviations from experiment that are less than 2 kcal/mol. The structures and vibrational frequencies that are generated in the course of these calculations are in good agreement with experimental data. Detailed comparisons with respect to structural types indicate that the present computational models are likely to generate useful data for complex models of combustion and pyrolysis of chemical warfare materials.

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“…The calculated bond lengths and angles are in very good agreement with experimental observations as listed in Table 1 from electron diffraction [27][28][29] or microwave spectroscopy. 30,31 Vertical excitation energies have been calculated for the optimized ground state geometry given in Table 1. No Rydberg excitations are expected below 8 eV.…”

Section: B Theoretical Resultsmentioning

confidence: 99%

Photodissociation dynamics of SOCl₂

Chichinin¹,

Einfeld²,

Gericke³

et al. 2005

Phys. Chem. Chem. Phys.

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New theoretical and experimental results for the ultraviolet photodissociation dynamics of thionyl chloride (SOCl2) are presented and combined with existing data from a variety of sources in order to provide a unified view of the photodissociation dynamics of SOC12. Time-dependent density functional theory on the basis of the hybrid-type B3LYP functional was employed to calculate vertical excitation energies for the SOCl2 parent molecule up to 6.3 eV. Three-dimensional (3D) imaging of photofragments was performed for a dissociation wavelength of 235 nm. Atomic chlorine fragments were observed in the 2P(3/2) ground state [Cl] and the 2P(1/2) excited spin-orbit state [Cl*] by employing resonance enhanced multi-photon ionization (REMPI) and time-of-flight (TOF) techniques. State-specific speed distributions and the speed dependence of the beta anisotropy parameter were obtained from the full 3D momentum vector distribution by appropriate projection methods. Bimodal speed distributions for both spin-orbit states are evidence of a competition between the radical (SOCl2 --> SOCl + Cl/Cl*) and the three-body decay channel (SOCl2 --> SO + 2 Cl/Cl*). No evidence of the molecular fragmentation channel (SOCl2 --> SO + Cl2) was found. With increasing fragment speed the beta anisotropy parameter increases from 0.1 to 0.85 and 0.68 for Cl and Cl*, respectively, suggesting fragmentation via an excited A' state for slow fragments and via an A" state for fast fragments. The calculations allow for the first time to interpret all previous and new experimental data for the ultraviolet photodissociation of SOCl2 by assuming simultaneous excitation of several excited electronic states giving rise to competing dissociation channels.

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Microwave spectrum and molecular structure of thionyl chloride

Cited by 17 publications

References 9 publications

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

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

Computational Tests of Quantum Chemical Models for Structures, Vibrational Frequencies, and Heats of Formation of Molecules with Phosphorus and Sulfur Atoms

Photodissociation dynamics of SOCl₂

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Microwave spectrum and molecular structure of thionyl chloride

Cited by 17 publications

References 9 publications

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

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

Computational Tests of Quantum Chemical Models for Structures, Vibrational Frequencies, and Heats of Formation of Molecules with Phosphorus and Sulfur Atoms

Photodissociation dynamics of SOCl2

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Photodissociation dynamics of SOCl₂