Computational Investigation of Isomeric and Conformeric Structures of Methyl Fluoroperoxide and Fluoromethyl Fluoroperoxides

The ab initio calculations for fluoromethyl fluoroperoxides have been carried out using MP2/6-311G(d,p) and B3LYP/6-311++G(d,p) method. The structural optimizations were performed for several isomers and conformers of methyl fluoroperoxide, $CH_3OOF$ and the vibrational frequencies were calculated. The most stable conformer of $CH_3OOF$ is skew form and has fairly short O-O bond distance. The trans and cis conformers have 8-12 kcal/mol higher energies than skew form and the other isomers are very unstable. The structures of $CH_2FOOF$, $CHF_2OOF$ and $CF_3OOF$ are also optimized and vibrational frequencies were calculated. These molecules also have skew forms as the lowest energy conformers. The O-O bond distances are longer and C-O bond distances are shorter than $CH_3OOF$, but the structural parameters are almost independent of the number of fluorine atoms in methyl group.

Methyl fluoroperoxide와 fuoromethyl fluoroperoxides의 conformers와 isomers 구조에 대한 이론연구

Methyl hydro-peroxide의 methyl group과 O-H에 F를 치환 시킨 fluoromethyl fluoroperoxide($CH_nF_{3-n}OOF$)의 안정한 conformers와 isomers에 대하여 MP2/6-311G(d,p) 방법과 B3LYP/6-311++G(d,p) 방법으로 최적화 계산을 수행하였고 vibrational frequencies를 구하였다. $CH_3OOF$와 $CH_2FOOF$, $CHF_2OOF$, $CF_3OOF$ 분자 모두 가장 안정한 형태는 skew 구조로 나타났으며 $CH_3OOH$와 비교할 때 대단히 짧은 O-O 결합길이를 갖는다. Trans, cis conformers의 경우 skew 형태보다 8-12 kcal/mol 정도 높은 에너지를 갖으며 O-O 결합길이는 훨씬 길어진다. $CH_2FOOF$, $CHF_2OOF$, $CF_3OOF$ 분자들은 methyl group의 F에 의한 induction 효과로 짧은 C-O 결합길이를 갖고 O-F 결합길이는 길어지나 치환된 F 원자의 수에 따른 구조변화는 그리 크지 않다.