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

Iwano, Sakae

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https://hdl.handle.net/2142/91186 Copy

Description

Title

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

Author(s)

Iwano, Sakae

Contributor(s)

• Hirota, Eizi
• Kawashima, Yoshiyuki

Issue Date

2016-06-22

Keyword(s)

Clusters/Complexes

Abstract

We have systematically investigated the van der Waals complexes consisting of the one from each of the two groups: (Rg, CO, \chem{N_2} or \chem{CO_2}) and (dimethyl ether, dimethyl sulfide, ethylene oxide or ethylene sulfide), by using Fourier transform microwave spectroscopy supplemented by ab initio MO calculations, in order to understand the dynamical behavior of van der Waals complexes and to obtain information on the potential function to internal motions in complexes.\footnote{Y. Kawashima, A. Sato, Y. Orita, and E. Hirota, ${J. Phys. Chem. A}$ \bf{2012} \it{116} \rm{1224}} Two examples of the \chem{N_2} complex were investigated: \chem{N_2}-DME (dimethyl ether), for which we reported a preliminary 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}} In the present study we focused attention to the \chem{N_2}-ES (ethylene sulfide) complex. We have detected two sets of the ${b}$-type transitions for the \chem{^{15}N_2}-ES in ortho and para states, and have analyzed them by using the asymmetric-rotor program of ${A}$-reduction. In contrast with the \chem{N_2}-EO, for which each of the ortho and para states were found split into a strong/weak pair, only some transitions of the \chem{^{15}N_2}-ES were accompanied by two or three components. The observed spectra of the \chem{^{14}N_2}-ES were complicated because of hyperfine splittings due to the nuclear quadrupole coupling of the two nitrogen atoms. We concluded that the \chem{N_2} moiety was located in the plane perpendicular to the C-S-C plane and bisecting the CSC angle of the ES. Two isomers were expected to exist for \chem{^{15}NN}-ES, one with \chem{^{15}N} in the inner and the other in the outer position, and in fact two sets of the spectra were detected. 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.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

En

Permalink

http://hdl.handle.net/2142/91186

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Copyright 2016 by the authors

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