The high-resolution rotational and torsional spectra of HSSH

Urban, Štěpán; Herbst, Eric; Mittler, P.; Winnewisser, G.; Yamada, Kōichi; Winnewisser, M.

doi:10.1016/0022-2852(89)90177-x

Cited by 41 publications

(20 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[36]. Torsional tunneling splittings for higher torsional states have also been determined, either experimentally or theoretically [33] [35] [37 ± 40]. Moreover, an increased torsional splitting in the millimeter-wave rotational spectra of an excited vibrational state was observed, and possible mechanisms for this increase were discussed [37] [41].…”

mentioning

confidence: 96%

See 1 more Smart Citation

Mode Selective Stereomutation and Parity Violation in Disulfane Isotopomers H2S2, D2S2, T2S2

Gottselig

Luckhaus

Qüack

et al. 2001

HCA

View full text Add to dashboard Cite

Dedicated to Edgar Heilbronner on the occasion of his 80th birthdayWe report quantitative calculations of stereomutation tunneling in the disulfane isotopomers H 2 S 2 , D 2 S 2 , and T 2 S 2 , which are chiral in their equilibrium geometry. The quasi-adiabatic channel, quasi-harmonic reaction path Hamiltonian approach used here treats stereomutation including all internal degrees of freedom. The torsional motion is handled as an anharmonic reaction coordinate in detail, whereas all the remaining degrees of freedom are taken into account approximately. We predict how stereomutation is catalyzed or inhibited by excitation of the various vibrational modes. The agreement of our theoretical results with spectroscopic data from the literature on H 2 S 2 and D 2 S 2 is excellent. We furthermore predict the influence of parity violation on stereomutation as characterized approximately by the ratio (DE pv /DE AE ) of the (local or vibrationally averaged) parity violating potential DE pv and the tunneling splittings DE AE in the symmetrical case. This ratio is exceedingly small for the reference molecules H 2 O 2 and D 2 O 2 , and still very small (2´10 À6 cm À1 ) for H 2 S 2 , which, thus, all exhibit essentially parity conservation in the dynamics. However, for D 2 S 2 it is ca. 0.002, and for T 2 S 2 it is ca. 1, which seems to be the first case where such intermediate mixing through parity violation is quantitatively predicted for spectroscopically accessible molecules. The consequences for the spectroscopic detection of molecular parity violation are discussed briefly also in relation to other molecules.

show abstract

mentioning

confidence: 96%

“…They are among the simplest prototypes for stereomutation, performing a large amplitude motion ± internal rotation, i.e., torsion around the SÀS bond. The barriers for stereomutation between the enantiomers of H 2 S 2 were determined experimentally [33] and theoretically [34] to be rather high, for the cisbarrier ca. 2800 cm À1 and for the trans-barrier ca.…”

mentioning

confidence: 99%

Mode Selective Stereomutation and Parity Violation in Disulfane Isotopomers H2S2, D2S2, T2S2

Gottselig

Luckhaus

Qüack

et al. 2001

HCA

View full text Add to dashboard Cite

show abstract

“…For HS34SH this effect is very small and there fore not observable. However both c-and b-type spec tra have been observed for HSSD [7] and very recently also for DS34SD which will be discussed elsewhere.…”

Section: Rotational Spectrummentioning

confidence: 79%

“…The rotational spectrum of disulfane, HSSH has been studied in a series of papers [1][2][3][4][5][6] and recently work has been resumed with the aim of understanding some of the subtle details of the HSSH spectrum, its barrier to internal rotation and its isotopic species [7], [8]. In addition it is now highly desirable and possible to have a full substitution structure of disulfane avail able, which can be compared with the ongoing theo retical chemistry ab-initio structural calculations.…”

Section: Introductionmentioning

confidence: 99%

Submillimeter Wave Spectrum of HS³⁴SH

Mittler

Winnewisser

Yamada

1989

Zeitschrift Für Naturforschung A

View full text Add to dashboard Cite

show abstract

“…Although the fundamentals of the internal rotation spectrum are the same (e.g., the staggering of the energy levels) for both molecules, the observed effects displayed by the spectra are rather different. The reason for this behavior is to be seen in the trans-barriers of the two molecules, i.e., 2037 cm −1 for H 2 S 2 and 387 cm −1 for H 2 O 2 (see e.g., Herbst and Winnewisser [1], Urban et al [2], and Flaud et al [3]). It is thus of interest to improve our knowledge of the torsion-rotation spectrum that occurs in the microwave and far infrared regions.…”

Section: Introductionmentioning

confidence: 99%