Dynamics of I(2P½) production from fluorinated alkyl iodides at 266,280,and ~305 nm

Kavitha, K. ; Das, Puspendu K. (2000) Dynamics of I(2P½) production from fluorinated alkyl iodides at 266,280,and ~305 nm Journal of Chemical Physics, 112 (19). pp. 8426-8431. ISSN 0021-9606

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Official URL: http://jcp.aip.org/jcpsa6/v112/i19/p8426_s1?isAuth...

Related URL: http://dx.doi.org/10.1063/1.481445


In this paper, we present I(2P½) quantum yield, φ from the gas phase photodissociation of a series of perfluoroalkyl iodides at three different wavelengths 266, 280, and ~305 nm. The iodine atoms in the ground I(2P3/2) and spin-orbit excited I(2P½) states were monitored directly by a two photon laser induced fluorescence scheme. The I quantum yields for the fluorinated alkyl iodides are found to be much higher than their corresponding alkyl iodide analogs over the entire A band. However, Φ remains more or less unchanged as a function of photolysis wavelength for the perfluoroalkyl iodides with the exception of CF3I in which it drops monotonically as a function of wavelength. Unlike in normal alkyl iodides, branching at the a position does not affect the φ in perfluoroalkyl iodides. The prediction of I yield using the one dimensional Landau-Zener soft-radical-impulse model is opposite to what is seen from our measurements. In all the fluorinated alkyl iodides, the CF3 in-plane rocking mode which can take the initially excited 3Q0 state to the 1Q1 state through the crossing region appears to be weakly coupled to the C-I stretch resulting in low yield of I atom in the dissociation process.

Item Type:Article
Source:Copyright of this article belongs to American Institute of Physics.
Keywords:Organic Compounds; Photodissociation; Ground States; Spin-orbit Interactions; Excited States; Fluorescence; Photoluminescence; Two-photon Spectra
ID Code:86340
Deposited On:09 Mar 2012 10:40
Last Modified:09 Mar 2012 10:40

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