Journal of the Korean Electrochemical Society (전기화학회지)

The Korean Electrochemical Society (한국전기화학회)
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Structural Analysis of Species in NbCI5-EMIC Room-Temperature Molten Salt with Raman Spectroscopic Measurement and Ab Initio Molecular Orbital Calculation

  • Koura, Nobuyuki (Faculty of Science and Technology, Tokyo University of Science) ;
  • Matsuzawa, Hidenori (Faculty of Engineering, Chiba Institute of Technology) ;
  • Kato, Tomoki (Faculty of Science and Technology, Tokyo University of Science) ;
  • Idemoto, Yasushi (Faculty of Science and Technology, Tokyo University of Science) ;
  • Matsumoto, Futoshi (Faculty of Science and Technology, Tokyo University of Science)
  • Published : 2002.11.01
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Abstract

The structure of species formed in $NbCI_5-I-ethyl-3-methylimidazolium$ chloride (EMIC) room-temperature molten salt (RTMS) was examined with the Raman spectroscopic measurement and ab initio molecular orbital calculation. The equilibrium structures of $NbCl_5,\;NbCl_6^-,\;Nb_2CI_{10},\;Nb_2CI_{11}^-,\;Nb_3CI_6^-,\;NbCI_6^--EMI^+\;(in\;which\;NbCI_6^-$ anion approaches $EMI^+$ cation with strong interaction) and $Nb_2CI_{11}^--EMI^+$ were obtained with the HF/LANL2DZ level of calculation. The harmonic frequencies at each equilibrium structure were compared with Raman spectra. The harmonic frequencies of $NbCI_6^--EMI^+,\; Nb_2CI_{11}^--EMI^+,\;and\;Nb_2CI_{10}$ were in good agreement with the Raman spectra of RTMS melts. In the $NbCI_5-EMIC RTMS$, the main species were $NbCI_6^-\;and\;EMI^+$. In the $NbCl_5-EMIC$ RTMS added $NbCl_5\;over\;50mol\%$, small amount of $Nb_2CI_{11}^-\;and\; Nb_2CI_{10}$ were also formed. The structures of anions and cation in the RTMS distorted from free ions with Coulomb force.

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