Direct observation of the intermediate radical in the photodissociation of 1, 3-cyclohexane dinitrite. Issue 35 (28th August 2019)

• Record Type: Journal Article
• Authors: Qin, Tai; Xue, Junfei; Huo, Dayujia; Zu, Lily
• Is Part Of: Physical chemistry chemical physics. Volume 21:Issue 35(2019)
• Page Start: 19359
• Page End: 19364
• Publication Date: 2019-08-28
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c9cp03895g
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The two-step photodissociation mechanism of 1, 3-cyclohexane dinitrite is confirmed by observation of the laser-induced fluorescence spectrum of the intermediate 3-nitrosooxy cyclohexoxy radical. Abstract : A two-step photodissociation mechanism was proposed in the literature for dinitrites in the absence of direct evidence of the intermediate species. In this work, photodissociation dynamics of cis and trans 1, 3-cyclohexane dinitrites are investigated by laser-induced fluorescence (LIF) spectroscopy and theoretical calculation methods. Observation of the fluorescence spectra of the 3-nitrosooxy cyclohexoxy radical provides direct experimental evidence that the intermediate species exists. The results indicate that photodissociation of dinitrites indeed follows a two-step mechanism, i.e. one of the O–NO bonds of the molecule breaks first upon 355 nm laser photolysis and generates an alkoxy radical (RO) plus NO; the alkoxy radical further dissociates in the secondary dissociation step and produces small fragments such as vinoxy etc.