DIMETHYL SULFIDE-DIMETHYL ETHER AND ETHYLENE OXIDE-ETHYLENE SULFIDE COMPLEXES INVESTIGATED BY FOURIER TRANSFORM MICROWAVE SPECTROSCOPY AND AB INITIO CALCULATION

Kawashima, Yoshiyuki

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https://hdl.handle.net/2142/79066 Copy

Description

Title

DIMETHYL SULFIDE-DIMETHYL ETHER AND ETHYLENE OXIDE-ETHYLENE SULFIDE COMPLEXES INVESTIGATED BY FOURIER TRANSFORM MICROWAVE SPECTROSCOPY AND AB INITIO CALCULATION

Author(s)

Kawashima, Yoshiyuki

Contributor(s)

• Hirota, Eizi
• Mase, Takayuki
• Tatamitani, Yoshio

Issue Date

25-Jun-15

Keyword(s)

Clusters/Complexes

Abstract

"The ground-state rotational spectra of the dimethyl sulfide-dimethyl ether (DMS-DME) and the ethylene oxide and ethylene sulfide (EO-ES) complexes were observed by Fourier transform microwave spectroscopy, and $a$-type and $c$-type transitions were assigned for the normal, $^{34}$S, and three $^{13}$C species of the DMS-DME and $a$-type and $b$-type rotational transitions for the normal, $^{34}$S, and two $^{13}$C species of the EO-ES. The observed transitions were analyzed by using an $S$-reduced asymmetric-top rotational Hamiltonian. The rotational parameters thus derived for the DMS-DME were found consistent with a structure of $C_{rm{s}}$ rm{symmetry with the DMS bound to the DME by two C-H(DMS)---O and one S---H-C(DME) hydrogen bonds. The barrier height} $V$$_{3}$ to internal rotation of the ""free"" methyl group in the DME was determined to be 915.4 (23) wn, which is smaller than that of the DME monomer, 951.72 (70) wn,footnote{ Y. Niide and M. Hayashi, it{J. Mol. Spectrosc}. bf{220}rm{, 65-79 (2003).}} and larger than that of the DME dimer, 785.4 (52) wn.footnote{ Y. Tatamitani, B. Liu, J. Shimada, T. Ogata, P. Ottaviani, A. Maris, W. Caminati, and J. L. Alonso, it{J. Am. Chem. Soc.} bf{124}rm{, 2739-2743 (2002).}} For the EO-ES complex the observed data were interpreted in the terms of an antiparallel $C_{rm{s}}$ geometry with the EO bound to the ES by two C-H(ES)---O and two S---H-C(EO) hydrogen bonds. We have applied a natural bond orbital (NBO) analysis to the DMS-DME and EO-ES to calculate the stabilization energy CT (= $Delta$$E$$sigma$$sigma$*), which were closely correlated with the binding energy $E_{rm{B}}$, as found for other related complexes."

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

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http://hdl.handle.net/2142/79066

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