Productions of I, I*, and C2H5 in the A-band photodissociation of ethyl iodide in the wavelength range from 245 to 283 nm by using ion-imaging detection.

J Chem Phys

State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan, Beijing 430071, People's Republic of China.

Published: February 2007

AI Article Synopsis

  • The study explores the photodissociation dynamics of ethyl iodide in the A band by analyzing ion images produced through resonance-enhanced multiphoton ionization at various wavelengths between 245 and 283 nm.
  • It identifies two main photodissociation channels that generate iodine fragments with different energy states and outlines a competitive ionization dissociation channel for wavelengths below 266 nm.
  • The research also reveals that the branching ratios for the dissociation products and their anisotropy parameters indicate the involvement of specific electronic states, while the influence of a heavier ethyl group on iodine production remains minimal compared to methyl iodide.

Article Abstract

Photodissociation dynamics of ethyl iodide in the A band has been investigated at several wavelengths between 245 and 283 nm using resonance-enhanced multiphoton ionization technique combined with velocity map ion-imaging detection. The ion images of I, I(*), and C(2)H(5) fragments are analyzed to yield corresponding speed and angular distributions. Two photodissociation channels are found: I(5p (2)P(3/2))+C(2)H(5) (hotter internal states) and I(*)(5p (2)P(1/2))+C(2)H(5) (colder). In addition, a competitive ionization dissociation channel, C(2)H(5)I(+)+h nu-->C(2)H(5)+I(+), appears at the wavelengths <266 nm. The I/I(*) branching of the dissociation channels may be obtained directly from the C(2)H(5) (+) images, yielding the quantum yield of I(*) about 0.63-0.76, comparable to the case of CH(3)I. Anisotropy parameters (beta) determined for the I(*) channel remain at 1.9+/-0.1 over the wavelength range studied, indicating that the I(*) production should originate from the (3)Q(0) state. In contrast, the beta(I) values become smaller above 266 nm, comprising two components, direct excitation of (3)Q(1) and nonadiabatic transition between the (3)Q(0) and (1)Q(1) states. The curve crossing probabilities are determined to be 0.24-0.36, increasing with the wavelength. A heavier branched ethyl group does not significantly enhance the I(5p (2)P(3/2)) production from the nonadiabatic contribution, as compared to the case of CH(3)I.

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http://dx.doi.org/10.1063/1.2435341DOI Listing

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