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Structures and Barrier Heights for the Internal Rotation of Ethyl Halides Caculated by ab initio Methods
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  • Structures and Barrier Heights for the Internal Rotation of Ethyl Halides Caculated by ab initio Methods
  • Structures and Barrier Heights for the Internal Rotation of Ethyl Halides Caculated by ab initio Methods
저자명
Ryu. Ung-Sik,Lee. Yoon-Sup
간행물명
Bulletin of the Korean Chemical Society
권/호정보
1994년|15권 3호|pp.221-227 (7 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

The barrier heights of the internal rotations for ethyl halides calculated by ab initio methods differ from those of experiments by more than 0.2 kcal/mol. The use of basis sets larger than the $6-31G^{ast}$ set and the inclusion of correlation do not improve the agreement between the calculated and experimental values. The zero-point vibration corrections are substantial in the HF calculations with $6-31G^{ast}$ basis sets, but become negligible in the MP2 calculations with $6-311G^{{ast}{ast}}$ basis sets for $C_2H_5F;and;C_2H_5Cl$. It is shown that the rigid rotor approximation and the assumed shape of the potential curve as a cos2${ heta}$ curve could also be the sources of discrepancies between calculated and experimental values. Higher order perturbation corrections narrow the gap between experimental and theoretical values, but there still remains about 10% overestimate of 0.3 kcal/mol. Optimized geometries from the HF and MP2 calculations are in good agreement with those from experiments. Dipole moments calculated from the MP2 densities show slightly better agreement with experiments than those from the HF densities.