Photodissociation of van der Waals clusters of isoprene with oxygen, C{sub 5}H{sub 8}-O{sub 2}, in the wavelength range 213-277 nm
- Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 ED Nijmegen (Netherlands)
- Institute of Chemical Kinetics and Combustion, Institutskaja Street 3, Novosibirsk 630090 (Russian Federation) and Novosibirsk State University, Pirogova street 2, Novosibirsk 630090 (Russian Federation)
The speed and angular distribution of O atoms arising from the photofragmentation of C{sub 5}H{sub 8}-O{sub 2}, the isoprene-oxygen van der Waals complex, in the wavelength region of 213-277 nm has been studied with the use of a two-color dissociation-probe method and the velocity map imaging technique. Dramatic enhancement in the O atoms photo-generation cross section in comparison with the photodissociation of individual O{sub 2} molecules has been observed. Velocity map images of these 'enhanced' O atoms consisted of five channels, different in their kinetic energy, angular distribution, and wavelength dependence. Three channels are deduced to be due to the one-quantum excitation of the C{sub 5}H{sub 8}-O{sub 2} complex into the perturbed Herzberg III state ({sup 3}{Delta}{sub u}) of O{sub 2}. This excitation results in the prompt dissociation of the complex giving rise to products C{sub 5}H{sub 8}+O+O when the energy of exciting quantum is higher than the complex photodissociation threshold, which is found to be 41740 {+-} 200 cm{sup -1} (239.6{+-}1.2 nm). This last threshold corresponds to the photodissociation giving rise to an unexcited isoprene molecule. The second channel, with threshold shifted to the blue by 1480 {+-} 280 cm{sup -1}, corresponds to dissociation with formation of rovibrationally excited isoprene. A third channel was observed at wavelengths up to 243 nm with excitation below the upper photodissociation threshold. This channel is attributed to dissociation with the formation of a bound O atom C{sub 5}H{sub 8}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}O + O and/or to dissociation of O{sub 2} with borrowing of the lacking energy from incompletely cooled complex internal degrees of freedom C{sub 5}H{sub 8}{sup *}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}{sup *}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}+ O + O. The kinetic energy of the O atoms arising in two other observed channels corresponds to O atoms produced by photodissociation of molecular oxygen in the excited a {sup 1}{Delta}{sub g} and b {sup 1}{Sigma}{sub g}{sup +} singlet states as the precursors. This indicates the formation of singlet oxygen O{sub 2}(a {sup 1}{Delta}{sub g}) and O{sub 2}(b {sup 1}{Sigma}{sub g}{sup +}) after excitation of the C{sub 5}H{sub 8}-O{sub 2} complex. Cooperative excitation of the complex with a simultaneous change of the spin of both partners {sup 1}X-{sup 3}O{sub 2}+h{nu}{yields}{sup 3}X-{sup 1}O{sub 2}{yields}{sup 3}X +{sup 1}O{sub 2} is suggested as a source of singlet oxygen O{sub 2}(a {sup 1}{Delta}{sub g}) and O{sub 2}(b {sup 1}{Sigma}{sub g}{sup +}). This cooperative excitation is in agreement with little or no vibrational excitation of O{sub 2}(a {sup 1}{Delta}{sub g}), produced from the C{sub 5}H{sub 8}-O{sub 2} complex as studied in the current paper as well as from the C{sub 3}H{sub 6}-O{sub 2} and CH{sub 3}I-O{sub 2} complexes reported in our previous paper [Baklanov et al., J. Chem. Phys. 126, 124316 (2007)]. The formation of O{sub 2}(a {sup 1}{Delta}{sub g}) from C{sub 5}H{sub 8}-O{sub 2} was observed at {lambda}{sub pump}= 213-277 nm with the yield going down towards the long wavelength edge of this interval. This spectral profile is interpreted as the red-side wing of the band of a cooperative transition {sup 1}X-{sup 3}O{sub 2}+h{nu}{yields}{sup 3}X(T{sub 2})-{sup 1}O{sub 2}(a {sup 1}{Delta}{sub g}) in the C{sub 5}H{sub 8}-O{sub 2} complex.
- OSTI ID:
- 22098969
- Journal Information:
- Journal of Chemical Physics, Vol. 137, Issue 5; Other Information: (c) 2012 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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