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Theoretical Calculations of Infrared Bands of CH3+ and CH5+
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  • Theoretical Calculations of Infrared Bands of CH3+ and CH5+
저자명
Matin. Mohammad A.,Jang. Joonkyung,Park. Seung Min
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2013년|34권 7호|pp.2051-2055 (5 pages)
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

Existing theoretical calculations predict that infrared spectra of the two most fundamental reactive carbo-ions, methyl cation $CH{_3}^+$ with $D_{3h}$ symmetry and protonated methyl cation $CH{_5}^+$ with $C_s(I)$, $C_s(II)$, and $C_{2v}$ symmetries, appear together in the 7-${mu}m$ region corresponding to the C-H bending modes. Vibrational band profiles of $CH{_3}^+$ and $CH{_5}^+$ have been compared by ab initio calculation methods that use the basis sets of MP2/aug-cc-pVTZ and CCSD(T)/cc-pVTZ. Our results indicate that the bands of rotation-vibration transitions of $CH{_3}^+$ and $CH{_5}^+$ should overlap not only in the 3-${mu}m$ region corresponding to the C-H stretching modes but also in the 7-${mu}m$ region corresponding to the C-H bending modes. Five band intensities of $CH{_5}^+$ among fifteen vibrational transitions between 6 and 8 ${mu}m$ region are stronger than those of the ${ u}_2$ and ${ u}_4$ bands in $CH{_3}^+$. Ultimate near degeneracy of the two bending vibrations ${ u}_2$ and ${ u}_4$ of $CH{_3}^+$along with the stronger intensities of $CH{_5}^+$ in the three hydrogen scrambling structures may cause extreme complications in the analysis of the high-resolution carbo-ion spectra in the 7-${mu}m$ region.