( N 2 O ) 2 ⋅ SO 2 : Rotational spectrum and structure of the first van der Waals trimer containing sulfur dioxide

Abstract

Articles you may be interested inEffect of solvent on molecular conformation: Microwave spectra and structures of 2-aminoethanol van der Waals complexes Structure and properties of the weakly bound cyclic trimer ( H 2 O ) 2 HBr observed by rotational spectroscopy Rotational spectrum, structure and modeling of the SO 2 -CS 2 complex J. Chem. Phys. 110, 6804 (1999); 10.1063/1.478584Fourier-transform microwave spectrum, structure, harmonic force field, and hyperfine constants of sulfur chloride fluoride, ClSFThe trimer (N 2 O) 2 •SO 2 has been studied by Fourier transform microwave spectroscopy. The rotational constants for the normal species are Aϭ1369.1014(11) MHz, Bϭ1115.5816(11) MHz, and Cϭ730.5790(4) MHz. Five isotopomers of the complex have been studied, allowing a determination of its structure. The configuration aligns the centers-of-mass of the three monomers in an approximate equilateral triangle. The monomers twist relative to this plane so that the two N 2 O's are intermediate between T-shaped and crossed rather than the usual slipped-parallel planar. The SO 2 is oriented so that its oxygens are straddling one N 2 O ͑similar to the N 2 O•SO 2 dimer͒, while its sulfur is closest to the oxygen end of the other N 2 O. The dipole moment of ( 15 N 2 O) 2•SO 2 was measured, giving a ϭ0.606(1) D, b ϭ1.256(2) D, c ϭ0.058(2) D, and total ϭ1.396(2) D. A semiempirical model has been used to predict the trimer structure, and comparison is made with this model as well as with the dimer N 2 O•SO 2 .

Ab initioand DFT studies on van der Waals trimers: The OCS · (CO2)2complexes

“…In the recent literature, Kuczkowski and coworkers reported a number of trimer structures deduced from rotational spectra obtained using a Fourier transform microwave spectrometer with a pulsed supersonic nozzle source 7–14. As a general conclusion, these authors reported that trimer structures often resemble dimer‐like van der Waals interactions, although with differences in the interaction distances or angles or both.…”

“…Indeed, Kuczkowski and coworkers concluded that:8 (a) although the induction forces are expected to be small in systems with small dipole moments like OCS · (CO 2 ) 2 the induction contributions are needed to fine tune the details; (b) an optimal model to closely reproduce the physical system will probably need to account for anisotropy in the interaction; and (c) values for the parameters of the model that are appropriate for predicting accurate dimer structures are not necessarily appropriate for trimers 10. Thus, the recent success of the ORIENT model in reproducing SO 2 containing trimers contrasts sharply with its relatively poor performance in the case of a number of sulfur containing dimers 14…”

Infrared spectrum of the CS2 trimer: observation of a structure with D3 symmetry

“…7,8 The heterodimers OCS-CO 2 and OCS-N 2 O are planar as well. 9,10 Structures of many ternary complexes containing these [11][12][13][14][15][16][17][18][19] and other [20][21][22][23] linear molecules can best be described as distorted triangular cylinders with the three monomers aligned roughly parallel to one another. Although not planar, the faces of the trimers often bear close resemblance to the geometry of the corresponding isolated dimers, 16 indicating that two-body interactions may still be dominant in forming the trimer.…”

Theoretical Study of Formic Acid−Sulfur Dioxide Dimers

“…20,21 Lewis bases interact by transfer of lone pair electrons to the electropositive S atom; these include acetonitrile, 22 pyridine, 23 dimethyl ether, 24 and ammonia. 25 Finally, π-electronrich molecules, such as CO 2 , 26 OCS, 27 CS 2 , 28 SO 2 itself, [29][30][31] N 2 O, 32,33 and acetylene, 34,35 donate π-electrons to S.…”