University of Illinois Urbana-Champaign

Nitrogen molecule-dimethyl sulfide complex investigated by fourier transform microwave spectroscopy and ab initio calculation

Kawashima, Yoshiyuki

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603348.pptx

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https://hdl.handle.net/2142/91137

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Title
Nitrogen molecule-dimethyl sulfide complex investigated by fourier transform microwave spectroscopy and ab initio calculation
Author(s)
Kawashima, Yoshiyuki
Contributor(s)
  • Hirota, Eizi
  • Iwano, Sakae
Issue Date
2016-06-22
Keyword(s)
Clusters/Complexes
Date of Ingest
2017-01-26T21:38:24Z
Abstract
This paper presents an extension of the preceding talk on the FTMW spectroscopy of \chem{N_2}-ES (ethylene sulfide), namely the results on \chem{N_2}-DMS (dimethyl sulfide). We have previously investigated two \chem{N_2} complexes: \chem{N_2}-DME (dimethyl ether), for which we reported a prelimanary result,\footnote{Y. Kawashima, Y. Tatamitani, Y. Morita, and E. Hirota, ${61st International Symposium on Molecular Spectroscopy}$, TE10 (2006)} and \chem{N_2}-EO (ethylene oxide).\footnote{Y. Kawashima and E. Hirota, ${J. Phys. Chem. A}$ \bf{2013} \it{117} \rm{13855}} We have observed the ground-state rotational spectrum of the \chem{N_2}-DMS complex, i.e. $c$-type transitions in the frequency region from 5 to 24 GHz, which we assigned to the normal, \chem{^{15}N_2}-DMS, and \chem{^{15}NN}-DMS species of the \chem{N_2}-DMS. We have found both the ortho and para states for the \chem{^{14}N_2}-DMS and \chem{^{15}N_2}-DMS species. In the case of the \chem{^{15}N_2}-DMS, some transitions with $K_{a}$ = 2 and 3 were observed slightly split by the internal rotation of the two methyl tops of the DMS. The observed spectra of the \chem{^{15}N_2}-DMS were analyzed by using the XIAM program. In the case of the para state of the \chem{^{15}N_2}-DMS, three rotational and five centrifugal distortion constants with the $V_{3}$ barrier to the methyl group internal rotation, whereas, in the case of the ortho state of the \chem{^{15}N_2}-DMS, two more centrifugal distortion constants, $\Phi_{JK}$ and $\Phi_{KJ}$, were needed to reproduce the observed spectra. For the \chem{N_2}-DMS complex, we concluded that the \chem{N_2} moiety was located in a plane perpendicular to the C-S-C plane and bisecting the CSC angle of the DMS. \\ We have carried out ab initio molecular orbital calculations at the level of MP2 with basis sets 6-311++G(d, p), aug-cc-pVDZ, and aug-cc-pVTZ, to complement the information on the intracomplex motions obtained from the observed rotational spectra. We have applied a natural bond orbital (NBO) analysis to the \chem{N_2}-DMS and \chem{N_2}-ES to calculate the stabilization energy CT (=$\Delta E_{\sigma\sigma}$), which was closely correlated with the binding energy $E_{B}$, as found for other related complexes.
Publisher
International Symposium on Molecular Spectroscopy
Type of Resource
text
Genre of Resource
Conference Paper / Presentation
Language
En
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http://hdl.handle.net/2142/91137
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Copyright 2016 by the authors

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