Rotational and vibrational spectroscopy of sulphuryl chloride, sulphuryl fluoride and dimethyl sulphone

Chen, Junyi (1991) Rotational and vibrational spectroscopy of sulphuryl chloride, sulphuryl fluoride and dimethyl sulphone. Doctoral (PhD) thesis, Memorial University of Newfoundland.

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Abstract

The rotational and vibrational spectra of sulphuryl chloride, sulphuryl fluoride and dimethyl sulphone have been extensively studied. The molecular structures of all three molecules and the harmonic force fields of the first two molecules have been derived from the experimental data. Some nuclear quadrupole interactions, Fermi resonance and Coriolis interactions of these molecules have also been investigated. -- (1) Cl₂SO₂: The microwave spectra of nine isotopic species of sulphuryl chloride, namely ³⁵Cl₂³²S¹⁶O₂, ³⁵Cl³⁷Cl³²S¹⁶O₂, ³⁵Cl₂³²S¹⁸O₂, ³⁵Cl³⁷Cl³²S¹⁸O₂, ³⁵Cl₂³⁴S¹⁸O₂, ³⁵Cl³⁷Cl³⁴S¹⁸O₂, 37Cl₂³²S¹⁶O₂, ³⁵Cl₂³⁴S¹⁶O₂ and ³⁵Cl³⁷Cl³⁴S¹⁶O₂, were observed in the ground state over the frequency range from 12000MHz to 84000MHz. The rotational constants and quartic centrifugal distortion constants have been calculated from these spectra. The effective, substitution and scaled structures of this molecule were evaluated from the rotational constants. The nuclear quadrupole hyperfine structures of some transitions were measured. The nuclear quadrupole splittings of ³⁵Cl₂³²S¹⁶O₂ transitions have been analyzed to yield the nuclear quadrupole coupling constants of ³⁵Cl as: xaa =-33.25MHz, xbb =-6.97MHz, xcc = 40.22MHz and n = 1.42. The Raman spectra of ³⁵Cl₂³²S¹⁶O₂, ³⁵Cl₂³²S¹⁸O₂ and ³⁵Cl₂³⁴S¹⁸O₂ have also been observed in both the liquid and gas phases. A Fermi resonance between the v1 fundamental and the first overtone of the v₈ mode has been analyzed. A harmonic force field with thirteen force constants has been determined from the quartic centrifugal distortion constants and the vibrational frequencies. The harmonic force field has been used to obtain the average structure for this molecule. The ground state average structural parameters of ³⁵Cl₂³²S¹⁶O₂ are: rSO = 1.41347(11)4, rSCI = 2.01124(10)4, angleOSO = 123.129(15)°, angleCISCI = 100.126(7)°. -- (2) F₂SO₂: The microwave spectra of five isotopic species: F₂³²S¹⁶O₂, F₂³²S¹⁸O₂, F₂³²S¹⁶O¹⁸O, F₂³⁴S¹⁶O₂ and F₂³⁴S¹⁸O₂ have been measured in the ground state from 6000 to 120000MHz. A large number of satellite series were also investigated for F₂³²S¹⁶O₂ and F₂³²S¹⁸O₂ and have been assigned to five vibrationally excited state transitions ( v₃ = 1, v₄ = 1, v₅ = 1, v₇ = 1 and v₉ = 1) of F₂³²S¹⁶O₂ and four vibrationally excited state transitions ( v₄ = 1, v₅ = 1, v₇ = 1 and v₉ = 1 ) of F₂³²S¹⁸O₂. The spectra have been analyzed to yield values for the rotational constants and quartic centrifugal distortion constants for both the ground and excited states. The sextic centrifugal distortion constants of the F₂³²S¹⁸O₂ species have also been determined. An effective geometry has been obtained from the ground state rotational constants. The Coriolis interaction constant [symbol] was derived as 0.264 and 0.24 for F₂³²S¹⁶O₂ and F₂³²S¹⁸O₂ respectively. A complete harmonic force field, with seventeen force constants, has been determined from the quartic distortion constants and vibrational frequencies. The harmonic force constants have been used to calculate the average molecular structure of F₂³²S¹⁶O₂ in the ground state. The average structural parameters are: rso = 1.40176(13)4, rSF = 1.53608(16)A, angleoso = 124.907(20)°, angleFSF = 95/84(13)°. -- (3) (CH₃)₂SO₂ The microwave spectra of eight isotopic species, (¹²CH₃)₂³²S¹⁶O₂, (¹³CD₃)₂³²S¹⁶O₂, (¹²CH₃)₂³²S¹⁶O¹⁸O, (¹²CH₃)(¹²CH₂D)³²S¹⁶O₂(I), (¹³CH₃)₂³²S¹⁶O₂, (¹²CH₃)₂³⁴S¹⁶O₂, (¹²CH₃)(¹³CH₃)³²S¹⁶O₂, (¹²CH₃)(¹²CH₂D)³²S¹⁶O₂(II), were observed in the ground state over the frequency range from 40000 to 85000MHz. The rotational constants and quartic centrifugal distortion constants of the eight species have been derived from the experimental data. Effective and substitution structures have been obtained using the ground state rotational constants. The substitution structural parameters of (¹³CH₃)₂³²S¹⁶O₂ are: -- rso = I.4343(23)4, rsc = 1.7728(28)4, rCH(I) = 1.0839(9)4, rCH(lI) = 1.0858(2)4, angleoso = 120.14(19)°, angleCSC = 103.61(16)°, angleSCH(I) = 105.59(25)°, angleSCH(II) = 109.51(19)°, angleH(l)C(II) = 110.38(11)°, angleH(II)CH(II) = 111.61(5)°.

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