Theoretical investigation of unimolecular decomposition channels of furan4

✍ Scribed by Liu, Ruifeng; Zhou, Xuefeng; Zhai, Lei

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 417 KB
• Volume: 19
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/(sici)1096-987x(19980130)19:2<240::aid-jcc17>3.0.co;2-l

✦ Synopsis

Density functional theory and high-level ab initio calculations were carried out to investigate three unimolecular decomposition channels of furan. All equilibrium and transition state structures along the proposed decomposition channels are fully optimized by B3LYPr6-31G** and characterized at the same level of theory by vibrational and intrinsic reaction coordinate analyses. Relative energies of the optimized structures were evaluated Ž . at theoretical levels up to QCISD T r6-311qqG**. The theoretical results suggest that the unimolecular decomposition channel of isoxazole, proposed in an experimental study and implied to be the main decomposition channel of furan, is responsible only for the formation of HC CH and H O C O , minor 2 products of furan thermal decomposition. A new decomposition mechanism, proposed in the present study, is shown to be more likely responsible for the formation of CH C CH and CO, major products of furan thermal 3 decomposition.