Molecular constants of sulfur dichloride from microwave spectrum analysis

Abstract

In presenting the dissertation as a partial fulfillment of the requirements for an advanced degree from the Georgia Institute of Technology, I agree that the Library of the Institution shall make it available for inspection and circulation in accordance with its regulations governing materials of this type. I agree that permission to copy from, or to publish from, this dissertation may he granted hy the professor under whose direction it was written, or, in his absence, hy the Dean of the Graduate Division when such copying or publication is solely for scholarly purposes and does not involve potential financial gain. It is under stood that any copying from, or publication of, this dis sertation which involves potential financial gain will not he allowed without written permission.

Ab initio Study of the Electric Field Gradients in SCl2

“…Due to some measured transitions with near degeneracy, Merke and Dreizler also obtained a much more accurate off-diagonal coupling constant. The constant they found greatly improved the one reported earlier by Murray et al [4] who determined the off-diagonal coupling element through analysis with second-order perturbation theory and the assumption of the S-Cl internuclear axis as a principal axis. The knowledge of measured diagonal and off-diagonal coupling constants makes it possible to determine the principal axis system within the molecular geometry frame.…”

“…Recently, Merke and Dreizler [2] used waveguide microwave Fourier transform spectroscopy to reinvestigate the quadrupole hyperfine structure of sulfur dichloride. Because of the high resolution of the spectroscopy, the coupling constants obtained are more reliable compared with previous studies [3][4][5]. Due to some measured transitions with near degeneracy, Merke and Dreizler also obtained a much more accurate off-diagonal coupling constant.…”

“…Nevertheless, it appears to be converging at both the SCF and SDCI levels when better basis sets were used. With the 5s 4p 2d basis set, the SDCI dipole moment is obtained as 0.1755, which is larger than the value 0.14 reported by Murray et al [4] The angle between the NQCC principal axis and the S-Cl internuclear direction is small. Nevertheless, it has been predicted quite consistently to be around 1.5° (see Tables 1 and 2).…”

Millimeter-Wave Spectroscopy of Sulfur Dichloride

“…Taking into account the C 2v symmetry of the molecule, which makes f 11 ϭ f 22 and f 13 ϭ f 23 , then Eq. [1] can be reduced to the sum of four independent terms:…”

New Sulfenyl Chloride Chemistry: Synthesis, Reactions and Mechanisms toward Carbon-Carbon Double Bonds

“…The geometry of sulfur dichloride (SCl 2 ) has been determined using microwave spectroscopy [16,17] and electron diffraction [18]. The structure of methanesulfenyl chloride [19][20][21] (5) was also investigated by microwave spectroscopy, while the trichloro-(6) [22] and trifluoro-(7) [23] derivatives were examined with electron diffraction.…”