Analytical Science and Technology (분석과학)

The Korean Society of Analytical Sciences (한국분석과학회)
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Theoretical study on the structures and the electron affinities of cyclic perfluoroalkanes (c-PFA)

Cyclic perfluoroalkanes(c-PFA)의 분자구조 및 분광학적 성질에 관한 이론 연구

  • 정성엽 (한남대학교 생명나노과학대학 화학과) ;
  • 신창호 (KT&G 중앙연구원) ;
  • 김승준 (한남대학교 생명나노과학대학 화학과)
  • Received : 2012.12.28
  • Accepted : 2013.01.07
  • Published : 2013.02.25
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Abstract

The geometrical parameters, vibrational frequencies, and adiabatic electron affinities (AEAs) for c-$C_nF_{2n}$ (n=8, 9) and $C_{10}F_{18}$ (perfluorodecalin) have been investigated using various quantum mechanical techniques. The possible structures for the neutrals and anions of c-PFA are fully optimized and electron affinities are predicted using energy difference between the neutral and anion. The harmonic vibrational frequencies are also determined and zero-point vibrational energies (ZPVEs) are considered for the better prediction of the electron affinities. The electron affinities are predicted to be 1.18 eV for c-$C_8F_{16}$ (ortho), 1.37 eV for c-$C_9F_{18}$, and 1.38 eV for $C_{10}F_{18}$ (perfluorodecalin) at the MP2 level of theory after ZPVE correction.

본 연구는 c-$C_nF_{2n}$ (n=8, 9)과 $C_{10}F_{18}$ (perfluorodecalin)의 가능한 분자구조를 여러 이론 수준에서 최적화 하였으며, 각 화합물의 가장 안정한 분자구조 (global minimum)를 확인하고 전자 친화도를 계산하여 구조적 특성에 따른 전자 친화도와의 상호 연관성을 고찰하였다. 보다 정확한 전자 친화도를 계산하기 위하여 진동주파수를 계산하여 영점 진동 에너지를 보정하였으며, IR 스펙트럼을 예측하였다. 전자 친화도는 c-$C_8F_{16}$의 경우 ortho 위치에 두 개의 $-CF_3$ 치환기가 붙어있는 구조에 대하여 영점 진동 에너지를 보정한 MP2 이론 수준에서 1.18 eV로 계산되었으며, c-$C_9F_{18}$의 경우 하나의 $-CF_3$와 하나의 $-C_2F_5$ 치환기가 인접하여 붙어있는 구조에 대하여 1.37 eV로, 그리고 $C_{10}F_{18}$인 perfluorodecalin의 경우 1.38 eV로 예측되었다.

Keywords

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