Files in this item

FilesDescriptionFormat

application/vnd.openxmlformats-officedocument.presentationml.presentation

application/vnd.openxmlformats-officedocument.presentationml.presentation346081.pptx (1MB)
PresentationMicrosoft PowerPoint 2007

application/pdf

application/pdf943.pdf (24kB)
AbstractPDF

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
Subject(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.
Issue Date:25-Jun-15
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:ACS
Genre:CONFERENCE PAPER/PRESENTATION
Type:Text
Language:English
URI:http://hdl.handle.net/2142/79066
Date Available in IDEALS:2016-01-05


This item appears in the following Collection(s)

Item Statistics