Cartoni Antonella, Bolognesi Paola, Fainelli Ettore, Avaldi Lorenzo
Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza Università di Roma, P.le Aldo Moro 5, Roma 00185, Italy.
CNR-IMIP, Area della Ricerca di Roma 1, Monterotondo Scalo (Rm) 00015, Italy.
J Chem Phys. 2014 May 14;140(18):184307. doi: 10.1063/1.4874114.
In this paper an investigation of the photofragmentation of dihalomethanes CH2X2 (X = F, Cl, Br, I) and chlorinated methanes (CH(n)Cl(4-n) with n = 0-3) with VUV helium, neon, and argon discharge lamps is reported and the role played by the different halogen atoms is discussed. Halogenated methanes are a class of molecules used in several fields of chemistry and the study of their physical and chemical proprieties is of fundamental interest. In particular their photodissociation and photoionization are of great importance since the decomposition of these compounds in the atmosphere strongly affects the environment. The results of the present work show that the halogen-loss is the predominant fragmentation channel for these molecules in the VUV photon energy range and confirm their role as reservoir of chlorine, bromine, and iodine atoms in the atmosphere. Moreover, the results highlight the peculiar feature of CH2F2 as a source of both fluorine and hydrogen atoms and the characteristic formation of I2(+) and CH2(+) ions from the photofragmentation of the CH2I2 molecule.
本文报道了用真空紫外氦、氖和氩放电灯对二卤甲烷CH2X2(X = F、Cl、Br、I)和氯代甲烷(CH(n)Cl(4 - n),n = 0 - 3)进行光解离的研究,并讨论了不同卤素原子所起的作用。卤代甲烷是一类在多个化学领域中使用的分子,对其物理和化学性质的研究具有根本重要性。特别是它们的光解离和光电离非常重要,因为这些化合物在大气中的分解会强烈影响环境。目前工作的结果表明,在真空紫外光子能量范围内,卤素损失是这些分子的主要解离通道,并证实了它们作为大气中氯、溴和碘原子储存库的作用。此外,结果突出了CH2F2作为氟和氢原子来源的独特特性,以及CH2I2分子光解离形成I2(+)和CH2(+)离子的特征。