Rotational spectrum and structure of the OCS–(CO2)2 trimer

Peebles, Sean A.; Kuczkowski, Robert L.

doi:10.1063/1.477145

Cited by 32 publications

(64 citation statements)

References 24 publications

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“…Spectra. For ( 18 OCS) 3 , 21 a-type and 10 c-type transitions were observed, while for (O 13 CS) 3 22 a-type and 9 c-type transitions were observed. The frequencies of these transitions are given in Tables 1 and 2.…”

Section: Resultsmentioning

confidence: 72%

“…The resulting spectroscopic constants for both isotopes and the normal species are given in Table 3. For the (O 13 CS) 3 isotopomer, δ K was not well determined, so it was fixed at the value of δ K of the ( 18 OCS) 3 isotopomer. This improved the quality of the fit slightly and had little effect on the other distortion constants.…”

Section: Resultsmentioning

confidence: 99%

“…Line widths were approximately 30 kHz full width at half-maximum, and center frequencies were reproducible to about 4 kHz. A typical transition of the ( 18 OCS) 3 isotopomer had a signal-to-noise ratio of about 7 in 300 gas pulses, while transitions of the (O 13 CS) 3 isotopomer generally required about 500 gas pulses to obtain the same quality of signal. Several transitions of both species were considerably weaker, requiring about 1000 gas pulses to obtain a good signal-to-noise ratio.…”

Section: Methodsmentioning

confidence: 99%

“…The spectra of two isotopomers of (OCS) 3 were observed in the 5.5-12.0 GHz range on the Balle-Flygare-type Fourier transform microwave spectrometers 9 at the University of Michigan. 10,11 The ( 18 OCS) 3 isotopomer was generated by expanding a mixture of 1% 18 OCS and 99% first run He/Ne (10% He/90% Ne) into the evacuated spectrometer chamber through a General Valve Series 9 nozzle, while the (O 13 CS) 3 isotopomer was generated by expanding a similar 2% O 13 CS mixture into the spectrometer cavity through a modified Bosch fuel injector valve.…”

Section: Methodsmentioning

confidence: 99%

“…10,11 The ( 18 OCS) 3 isotopomer was generated by expanding a mixture of 1% 18 OCS and 99% first run He/Ne (10% He/90% Ne) into the evacuated spectrometer chamber through a General Valve Series 9 nozzle, while the (O 13 CS) 3 isotopomer was generated by expanding a similar 2% O 13 CS mixture into the spectrometer cavity through a modified Bosch fuel injector valve. The 18 OCS (93.4% 18 O) and O 13 CS (99% 13 C, 12% 18 O) were obtained from Isotec.…”

Section: Methodsmentioning

confidence: 99%

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The OCS Trimer: Isotopic Studies, Structure, and Dipole Moment

Peebles

Kuczkowski

1999

J. Phys. Chem. A

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The rotational spectra of ( 18 OCS) 3 and (O 13 CS) 3 have been assigned using a pulsed-nozzle Fourier transform microwave spectrometer. The data for these isotopic species have been combined with normal species data from a paper by Connelly et al. [Connelly, J. P., et al. Mol Phys. 1996, 88, 915] to determine the nine structural parameters of the trimer. The carbon atoms form a triangle with the axes of the monomer units roughly parallel to each other (barrel-like structure). The monomers have an antiparallel-like arrangement, with the dipole moment of one monomer opposing those of the other two monomers. The dipole moment of the complex has been measured, giving values of µ a ) 0.537(10) D, µ c ) 0.373(2) D, and µ total ) 0.653(8) D. The b component of the dipole moment was too small to determine from our data but is predicted to be about 0.02 D. The structure of (OCS) 3 has been compared with similar trimers involving linear triatomic molecules and with the OCS dimer. Semiempirical calculations have been performed on the (OCS) 3 system, and they show good qualitative agreement with the experimental structure.

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Section: Resultsmentioning

confidence: 72%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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The OCS Trimer: Isotopic Studies, Structure, and Dipole Moment

Peebles

Kuczkowski

1999

J. Phys. Chem. A

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

Valdés

Sordo

2002

J Comput Chem

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Ab initio calculations [MP2, MP4SDTQ, and QCISD(T)] using different basis sets [6-31G(d,p), cc-pVXZ (X = D, T, Q), and aug-cc-pVDZ] and density functional theory [B3LYP/6-31G(d,p)] calculations were carried out to study the OCS.(CO2)2 van der Waals trimer. The DFT has proved inappropriate to the study of this type of systems where the dispersion forces are expected to play a relevant role. Three minima isomers (two noncyclic and one cyclic) were located and characterized. The most stable isomer exhibits a noncyclic barrel-like structure whose bond lengths, angles, rotational constants, and dipole moment agree quite well with the corresponding experimental values of the only structure observed in recent microwave spectroscopic studies. The energetic proximity of the three isomers, with stabilization energies of 1442, 1371, and 1307 cm-1, respectively, at the CBS-MP2/cc-pVXZ (X = D, T, Q) level, strongly suggests that the two unobserved structures should also be detected as in the case of the (CO2)3 trimer where both noncyclic and cyclic isomers have been reported to exist. The many-body symmetry-adapted perturbation theory is employed to analyze the nature of the interactions leading to the formation of the different structures. The three-body contributions are small and stabilizing for the two most stable structures and almost negligible for the cyclic isomer.

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