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Matrix Photochemistry of Cycloheptatriene: Site Effects

机译:环庚三烯的基质光化学:位点效应

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摘要

An experimental study of CHT photolysis at 2537 A in argon and nitrogen (N_2) matrices is presented. The sole IR detectable product is identified as BCHD: bicyclo[3.2.0]hepta-2, 6-diene. It is found that CHT molecules trapped in spectroscopically distinct sites were converted to the product at different rates. In the initial stages of the photolysis, the population of some CHT trapping sites increased, indicating site population transfer. In the long run, however, all sites were deleted. Molecular dynamics simulations are performed to estimate the structure of the different sites, and together with a kinetic model, are used to account for the UV induced changes. A tentative energy level diagram of the system is offered, in an attempt to rationalize the total absence of toluene which is formed predominantly in the gas-phase irradiation of CHT at this wavelength. The "twin state" concept is instrumental in this rationalization.
机译:提出了在2537 A的氩气和氮气(N_2)基质中CHT光解的实验研究。唯一的红外可检测产物被鉴定为BCHD:双环[3.2.0]庚2-2、6-二烯。发现被困在光谱上不同的位点的CHT分子以不同的速率转化为产物。在光解的初始阶段,一些CHT捕获位点的种群增加,表明位点种群转移。但是从长远来看,所有站点都被删除了。进行分子动力学模拟以估计不同位点的结构,并与动力学模型一起用于解释紫外线引起的变化。提供该系统的暂定能级图,以试图合理地完全排除在该波长下CHT的气相照射中形成的甲苯的总量。 “孪生状态”概念在这种合理化中起了重要作用。

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