Photodissociation of partially fluorinated alkyl iodides in their A-band

Kavita, K. ; Das, Puspendu K. (2001) Photodissociation of partially fluorinated alkyl iodides in their A-band Journal of Physical Chemistry A, 105 (2). pp. 315-318. ISSN 1089-5639

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Photodissociation dynamics of partially substituted alkyl iodides with fluorine atoms at β and γ positions has been investigated. The iodine atoms in the ground I(2P3/2) and spin-orbit excited I(2P½) states produced in the ultraviolet photolysis of CF3CH2I, C6F13CH2CH2I, and C8F17CH2CH2I have been detected using a two photon laser induced fluorescence (TPLIF) scheme. The I quantum yield of the above iodides at 222, 236, 266, 280, and ~305 nm corresponding to the red and blue wings as well as the peak of their A-band absorption spectrum has been determined. The I yield from β and γ-substituted iodides is found to remain more or less unchanged as a function of excitation wavelength below 262 nm, which is the peak of their A-band. The observed dynamics at 222, 236, and 266 nm can be adequately described by the known Landau-Zener curve crossing model between the 3Q0 and 1Q1 states. However, at wavelengths above 262 nm, the measured I quantum yield of β and γ-substituted alkyl iodides reflects that the 3Q1 state has a significant contribution to the overall dynamics. The electronic effect exerted by fluorine on the dynamics appears to wither as the substitution moves further away from the C-I bond.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:10105
Deposited On:02 Nov 2010 09:52
Last Modified:30 May 2011 10:49

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