Effect of Initial Orientation on the Laser-Induced Cycloaddition Reaction of Benzene and Ethylene. (3rd November 2014)

• Record Type: Journal Article
• Authors: Yuan, Shuai; Hong, Huiling; Wang, Gang; Zhang, Wenying; Wu, Weifeng; Dou, Yusheng; Lo, Glenn V.
• Other Names: Li Fuli Academic Editor.
• Is Part Of: International journal of photoenergy. Volume 2014(2014)
• Publication Date: 2014-11-03
• Subjects: Photochemistry -- Periodicals; Photobiology -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Photochimie; Photobiologie; Chimie physique et théorique; Chemistry, Physical and theoretical; Photobiology; Photochemistry; Electronic journals; Periodicals; 541.35
• DOI: 10.1155/2014/850641
• Languages: English
• ISSNs: 1110-662X

Abstract

Abstract : The [2 + 2] photocycloaddition reaction of benzene and ethylene was investigated by semiclassical dynamics simulation and complete active space self-consistent field (CASSCF) ab initio calculations. Following laser excitation of the benzene molecule, two mechanisms were observed depending on the location of the second C of ethylene in relation to the hexagonal prism space defined by the first C and the plane of the benzene ring. Synchronous formation of two bonds was observed when the second C is outside the prism space; an asynchronous mechanism is observed otherwise. Charge transfer was observed only in the asynchronous mechanism; CASSCF calculations suggest that the asynchronous mechanism involves a barrierless path from the Frank-Condon point to a conical intersection, while the synchronous mechanism involves 0.8 eV barrier. These results are consistent with a higher quantum yield observed in the simulations for the asynchronous pathway.