VUV photodissociation dynamics of OClO: binary and triple dissociation

Dennis W. Hwang; Jim J. Lin; Yuan T. Lee; Xueming Yang

doi:10.1117/12.308413

15 May 1998 VUV photodissociation dynamics of OClO: binary and triple dissociation

Dennis W. Hwang, Jim J. Lin, Yuan T. Lee, Xueming Yang

Proceedings Volume 3271, Laser Techniques for State-Selected and State-to-State Chemistry IV; (1998) https://doi.org/10.1117/12.308413
Event: Optoelectronics and High-Power Lasers and Applications, 1998, San Jose, CA, United States

Abstract

Photodissociation of OClO at 157.6 nm excitation has been investigated using the photofragment transnational spectroscopic technique. Two distinctive chemical dissociation channels have been observed: one is the binary dissociation process, OClO + hv yields ClO + O; the other one is the triple dissociation process, OClO + hv yields Cl + O + O. The branching ratio of the binary dissociation channel to the triple dissociation channel is determined to be 0.59: 0.41. Bimodal vibrational distribution of the ClO product has been observed for the OClO yields ClO (X² (Pi) ) + O(³P, ¹D) channel, implying that two distinctive dissociation routes possibly exist in the binary dissociation process. The bimodal distribution is likely caused by the two dissociation pathways from two excited electronic states: the D(²A₁) and E(²B₁) states of OClO. These arguments are further supported by the results of the anisotropy parameter measurements for the binary dissociation channels. Experimental results also show that the OClO + hv yields ClO(X² (Pi) ) + O(¹S) and OClO + hv yields ClO(A ²(Pi) ) + O(³P) channels might also exist in addition to the ClO(X²(Pi) ) + O(³P, ¹D) channel. In the triple dissociation process, experimental results show that the main product channel is the OClO + hv yields Cl(²P) + O(¹D) + O(³P) channel, while the OClO + hv yields Cl(²P) + O(³P) + O(³P) channel is the minor one. The branching ratio of these two channels is determined to be 0.89:0.11. From the modeling of the time of flight spectra of the O atom product, it is believed that the triple dissociation process of OClO is a simultaneous process within the time scale of one rotation period.

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Dennis W. Hwang, Jim J. Lin, Yuan T. Lee, and Xueming Yang "VUV photodissociation dynamics of OClO: binary and triple dissociation", Proc. SPIE 3271, Laser Techniques for State-Selected and State-to-State Chemistry IV, (15 May 1998); https://doi.org/10.1117/12.308413

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KEYWORDS

Chemical species

Chlorine

Binary data

Molecules

Anisotropy

Molecular beams

Process modeling

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