Rotational spectrum and equilibrium structure of silanethione, H2SiS

Thorwirth, Sven; Gauß, Jürgen; McCarthy, Michael; Shindo, F.; Thaddeus, P.

doi:10.1039/b814558j

Cited by 22 publications

(17 citation statements)

References 33 publications

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“…Owing to their high reactivity, a few silanethiones (silicon-sulfur double bond compounds, RR Si=S) kinetically stabilized with bulky end groups (RR ) have been synthesized; 3 however, attempts to synthesize the parent species H 2 SiS were unsuccessful for a long time, 4 and H 2 SiS was only recently observed here in a supersonic molecular beam. 5 Another small silicon sulfide of general interest is disilicon sulfide, Si 2 S, which we have observed by Fourier transform microwave (FTM) spectroscopy in the same molecular beam as H 2 SiS (see Fig. 1).…”

Section: Introductionmentioning

confidence: 82%

Rotational spectra and equilibrium structures of H2SiS and Si2S

McCarthy

Gottlieb²,

Thaddeus³

et al. 2011

The Journal of Chemical Physics

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The rotational spectra of two small silicon sulfides, silanethione H(2)SiS and the disilicon sulfide ring Si(2)S, have been detected in the centimeter band by Fourier transform microwave spectroscopy of a molecular beam; lines of H(2)SiS were also observed in the millimeter band up to 377 GHz in a glow discharge. Precise rotational and centrifugal distortionconstants have been determined for the normal and a number of the more abundant rare isotopic species of both closed-shell molecules. Theoretical equilibrium (r(e)) structures of H(2)SiS and Si(2)S were derived from coupled-cluster calculations that included triple and quadruple excitations, core correlation, and extrapolation to the basis-set limit. The r(e) structures agree to within 5×10(-4) Å and 0.1(∘) with empirical equilibrium (r(e)(emp)) structures derived from the experimental rotational constants, combined with theoretical vibrational and electronic corrections. Both H(2)SiS and Si(2)S are good candidates for radioastronomical detection in the circumstellar shells of evolved carbon-rich stars such as IRC+10216, because they are fairly polar and are similar in composition to the abundant astronomical molecule SiS.

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Section: Introductionmentioning

confidence: 82%

Rotational spectra and equilibrium structures of H2SiS and Si2S

McCarthy

Gottlieb²,

Thaddeus³

et al. 2011

The Journal of Chemical Physics

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“…(4)) were found to be important in reproducing the rotational mixing caused by the anharmonic resonance, though they are 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 totally correlated and cannot be simultaneously determined. Therefore, we decided to fix W 389 at the value derived from the ab initio φ 389 normal coordinate cubic force constant [32], whereas W 389J was released in the least-squares fit.…”

Section: Observed Spectra and Analysismentioning

confidence: 99%

Submillimetre-wave spectrum of diacetylene and diacetylene-d2

Bizzocchi¹,

Esposti

Dore

2010

Mol. Phys.

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“…The experimental investigations presented herein were guided by highlevel coupled-cluster calculations at the same level of theory as that reported recently for silanethione, H 2 SiS. [13] Details concerning the approach used to treat electron-correlation and basis-set effects in quantum-chemical calculations in a quantitative manner are given below and can also be found in Ref. [14].HPSi was produced in the gas phase through a discharge of silane and phosphine in neon and then detected at high-[*] Dr.…”

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confidence: 99%

Bonding in the Heavy Analogue of Hydrogen Cyanide: The Curious Case of Bridged HPSi

et al. 2010

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The bonding of first-and second-row elements differ dramatically. The simplest unsaturated silicon hydrides Si 2 H 2 and Si 2 H 4 exhibit quite unusual geometries [1] compared to the analogous hydrocarbon molecules. For example, the most stable form of Si 2 H 2 is nonplanar with C 2v symmetry and two bridging H atoms, in sharp contrast to linear acetylene, HC CH. Phosphorus and nitrogen share many of the same bonding characteristics, but P prefers single over multiple bonds. For these reasons, it may be difficult to predict the most stable isomeric arrangement, even for a small molecule with a single P or Si atom and especially when it contains both.Silicon-phosphorus bonds are important in materials science [2] and organometallic chemistry. [3] Geometries for several-hundred larger molecules containing a phosphorussilicon single bond have been determined by X-ray crystallography, [4] but the uncertainties are typically 0.05 . With respect to phosphorus-silicon multiple bonds, it appears that sterically stabilized phosphasilenes [5] R 2 Si = PR' are the only compounds that have been isolated to date. The precise structures have been determined for only two of these species, using single-crystal X-ray crystallography.[6] Our knowledge of the SiÀP bond is therefore quite inadequate.Gas-phase investigations of phosphorus-silicon compounds have been hampered by their high reactivity; consequently the structures of only a few species with Si À P bond have been accurately characterized, [7] that is, with accuracies of at least 0.05 . Nevertheless, it should be noted that small molecules containing both elements are also of astronomical interest, because silicon-and phosphorus-bearing molecules [8j have been detected in the interstellar space by radio astronomy.HPSi is perhaps the simplest unsaturated compound to have a chemical bond between silicon and phosphorus. Quantum-chemical calculations and experimental investigations [9] have shown that linear structures are by far the most stable arrangements for HCN, HNC, and the heavier analogues HNSi and HCP. Until the present investigation, no experimental data were available for HPSi, but ab initio calculations [10][11][12] concluded that a bridged structure with a SiÀ P double bond (hereafter denoted HPSi) is more stable than linear HSiP. These calculations [12] also predict an energy difference, of the order of 10 kcal mol À1 , between these forms; a transition state lying 13 kcal mol À1 above HSiP connects the two isomers. Although hydrogen bonding occurs in silicon hydrides, no phosphorus-bearing molecules with this type of bonding are known.To determine the existence, geometry, and bonding of HPSi, a study has been undertaken to measure its rotational spectrum. Rotational spectroscopy is an ideal technique to study HPSi and other polar molecules because rotational frequencies are directly related to the moments of inertia along the three principal axes of the molecule. With sufficient isotopic substitutions, it is then possible to determine highly accurate molecular...

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Rotational spectrum and equilibrium structure of silanethione, H2SiS

Cited by 22 publications

References 33 publications

Rotational spectra and equilibrium structures of H2SiS and Si2S

Rotational spectra and equilibrium structures of H2SiS and Si2S

Submillimetre-wave spectrum of diacetylene and diacetylene-d2

Bonding in the Heavy Analogue of Hydrogen Cyanide: The Curious Case of Bridged HPSi

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