Molecular structure of cis- and trans-H2S3

doi:10.1016/S0022-2860(97)00030-6

Journal of Molecular Structure

Volumes 413–414, 30 September 1997, Pages 265-270

Dedicated to Professor Kozo Kuchitsu on the occasion of his 70th birthday.

https://doi.org/10.1016/S0022-2860(97)00030-6 Get rights and content

Abstract

The rotational spectra of cis- and trans-HSSSH have been complemented up to 670 GHz (^rQ₂₉ branch) and the spectra of several of its isotopomers have been recorded between 70 and 300 GHz. The derived rotational constants of HSSSH, H ³⁴SSSH, HS ³⁴SSH, HSSSD, and DSSSD provide the experimental basis for for deriving a substitution structure (r_s) for cis-HSSSH and and a r_ϵI structure for both species, i.e. cis- and trans-HSSSH. The r_ϵI bond distances and angles are for the cis-conformer: $R(SH) = 1.3435(14) A ̊$ , $R(SS) = 2.0530(1) A ̊$ , ∠SSH = 97.37(15)°, ∠SSS = 106.919(3)°, ∠SSS-SSH = 90.82(16)°. and for the trans-conformer: $R(SH) = 1.3435 (assumed) A ̊$ , $R(SS) = 2.0539(4) A ̊$ , ∠SSH = 97.2(7)°, ∠SSS = 107.02(2)°, ∠SSS-SSH = 87.7(4)°. These experimental structural results are in good agreement with ab initio calculations. The spectra show no effect of internal rotation, in agreement with a theoretical barrier estimate of ∼2900 cm⁻¹

References (12)

D. Mauer et al.
J. Mol. Struct.
(1988)
D. Mauer et al.
J. Mol. Spectrosc.
(1989)
G. Winnewisser
Vib. Spectrosc.
(1995)
S.P. Belov et al.
J. Mol. Spectrosc.
(1995)
D. Mauer et al.
Z. Naturforsch.
(1988)
M. Liedtke et al.
J. Phys. Chem.
(1993)

There are more references available in the full text version of this article.

Cited by (13)

Modelling of the torsional IR spectra of the HSSSH, DSSSH, and DSSSD molecules
2023, Computational and Theoretical Chemistry
Equilibrium configurations of trans- and cis- conformers of the HSSSH molecule (trisulfane), as well as the vibrational spectra of both conformers, were calculated at the MP2/Aug-cc-pVTZ, level of theory in the harmonic and anharmonic approximations. A more accurate analysis of torsional vibrations of thiol groups was performed by constructing 2D surfaces of a) potential energy, b) kinetic coefficients, and c) dipole moment components as functions of torsional coordinates of S-H groups. The values of b) and c) were calculated at the MP2/Aug-cc-pVTZ level of theory while the values of a) were calculated at the B3LYP/Aug-cc-pVTZ, MP2/cc-pVTZ, MP2/Aug-cc-pVTZ, MP2/cc-pVQZ, MP2/CBS(T,Q) and CCSD(T)/Aug-cc-pVTZ levels of theory. The energies of the stationary torsional states of the trisulfane molecule conformers were determined by numerically solving the vibrational Schrödinger equation of restricted dimensionality. The frequencies of torsional vibrations of S-H groups, as well as the splittings of torsional energy levels in trans- and cis-conformers due to tunneling between equivalent configurations of the molecule, were determined. The calculated values of tunneling frequencies in the ground torsional state of HSSSH and DSSSD trans-conformers (2.3 * 10⁻²² and 7.5 * 10⁻²⁷ cm⁻¹, respectively) are of particular interest due to the fact that trisulfane is considered to be one of the best candidates for establishing the effect of violation of parity conservation law in chiral molecules.
The rotational gas-phase spectrum of trans- and cis-HSSOH at 100 GHz
2009, Journal of Molecular Spectroscopy
We present the first pure rotational spectra of the two most stable conformers of oxatrisulfane, trans- and cis-HSSOH, in their vibrational ground state. For both conformers a-, b-, and c-type transitions have been recorded in the range from 75 to 120 GHz using an all solid-state spectrometer. More than 200 lines have been assigned for each conformer, most of them belonging to the $^{r} Q_{2}$ - and the $^{r} Q_{3}$ -branch of the perpendicular spectra. The least-squares fit analysis using a semirigid rotor Hamiltonian in S-reduction yields precise values for the ground-state rotational constants $A_{0} = 21 145.93422 (66), B_{0} = 4479.92301 (21), C_{0} = 3828.34269 (21)$ for cis-HSSOH, and $A_{0} = 21 071.08204 (75), B_{0} = 4490.04249 (34), C_{0} = 3833.20651 (35)$ for trans-HSSOH as well as centrifugal distortion parameters of quartic and sextic order. The ratio of the permanent dipole moment components $μ_{b} / μ_{c} = 0.29 (3)$ for cis-HSSOH and $μ_{b} / μ_{c} = 0.99 (3)$ for trans-HSSOH has been derived from measured line intensities. All experimentally derived molecular parameters are in very good agreement with high-level quantum-chemical calculations using coupled-cluster techniques, thus confirming the current understanding of the structure of oxasulfanes.
Experimental and theoretical studies on bis(chlorocarbonyl)trisulfane, ClC(O)SSSC(O)Cl
2009, Journal of Molecular Structure
Bis(chlorocarbonyl)trisulfane, ClC(O)SSSC(O)Cl, was prepared by the reaction of (CH₃)₂CHOC(S)SC(S)OCH(CH₃)₂ and SO₂Cl₂ at 65 °C. The compound was characterized and identified by vibrational spectroscopy, GC–MS, matrix isolation and photochemical studies as well as by quantum chemical calculations. Matrix photochemical studies and vibrational spectra were interpreted in terms of the presence of three forms with syn-gauche-gauche-syn (I), syn-(−)gauche-gauche-syn (II), and syn-gauche-gauche-anti (III) conformations. The syn and anti conformations correspond to the orientation of each CO group with respect to the adjacent SS bond, while the gauche form refers to the conformation around each of the SS bond. This result is in agreement with quantum chemical calculations which predict structures II and III to be higher in energy than conformer I by about 1.51/0.98 and 2.52/2.84 kcal/mol for the B3LYP/MP2 approximations in combination with the 6-31+G* basis set. An assignment of the liquid IR and Raman spectra is proposed for ClC(O)SSSC(O)Cl, as well as the possible mechanisms of the photolysis in Ar and N₂ matrices. The presence of ClC(O)SSCl as a photochemical product opens the possibility of further investigations for this family.
Rotational Spectra of the Thiosulfeno Radical, HSS and DSS, between 0.3 and 0.9 THz
2000, Journal of Molecular Spectroscopy
The rotational spectra of the HSS and DSS radicals were studied in selected regions between 331 and 883 GHz. The radicals were produced by discharging a gaseous mixture of hydrogen (or deuterium) and hydrogen sulfide in the cell. The observation of the b-type Q-branch and R-branch lines with K_a = 2–1 and 3–2 for HSS and DSS, respectively, as well as the a-type R-branch lines allowed the improvement and the determination of the molecular constants among them (in MHz) We have reevaluated the harmonic force field of HSS and the ground state average and approximate equilibrium structural parameters. For the latter, we obtained r(HS) = 135.23 pm, r(SS) = 196.03 pm, and ∠ = 101.74°. These results are compared with those from previous and own quantum chemical calculations as well as with results of related molecules.
Chapter 3 The quest for the equilibrium structure of molecules
1999, Vibrational Spectra and Structure
This chapter explores that the determination of molecular structures has been one of the objectives of high resolution spectroscopy for a long time. This technique, together with gas phase electron diffraction, is the only practical method available to study structures of molecules in the gaseous state. In that state at sufficiently low pressures, molecules are free from interactions with other species and can therefore be studied isolated from the environment. It discusses that modern high resolution molecular spectroscopy has a tremendous resolving power and precision. Conventional Stark effect modulated microwave spectroscopy has a typical resolution of 1 in 10⁵ and precision of 1 in 10⁶. A similar precision is achieved by high resolution Fourier transform infrared spectroscopy. Fourier transform microwave spectroscopy and laser based infrared spectroscopy have a precision close to 1 in 10⁸. If these spectroscopic methods are coupled with the supersonic molecular beam technique, the resolution approaches 1 in 10⁷. The chapter also discusses the theoretical models for fairly rigid molecules. With these models, the spectra observed for such molecules can be reproduced within the experimental precision. Many fitting parameters of these models—the spectroscopic constants—are obtained with high precision. Among them are the rotational constants, which sometimes have 8 or more significant digits. The chapter reviews the methods and techniques that are used to determine gas phase molecular structures from high resolution spectroscopic data. Principal techniques to obtain structures of molecules in the gas phase, electron diffraction are also discussed.
High-resolution FTIR spectroscopy of trisulfane HSSSH: A candidate for detecting parity violation in chiral molecules
2017, Physical Chemistry Chemical Physics

View all citing articles on Scopus

View full text

Molecular structure of cis- and trans-H2S3

Abstract

J. Mol. Struct.

J. Mol. Spectrosc.

Vib. Spectrosc.

J. Mol. Spectrosc.

Z. Naturforsch.

J. Phys. Chem.

Molecular structure of cis- and trans-H₂S₃