Extremely Rotationally Excited OH from Water (HOD) Photodissociation through Conical Intersection

Steven A. Harich; Xuefeng Yang; Xueming Yang; Richard N. Dixon

doi:10.1103/PhysRevLett.87.253201

Extremely Rotationally Excited OH from Water (HOD) Photodissociation through Conical Intersection

Steven A. Harich, Xuefeng Yang, Xueming Yang, and Richard N. Dixon

Phys. Rev. Lett. 87, 253201 – Published 29 November 2001

Abstract

Photodissociation of HOD from the $\tilde{B}$ state has been studied using the Rydberg “tagging” time-of-flight technique. Experimental results indicate that extreme rotational excitation in the $OH (X, v = 0)$ product ( $N$ up to 50 or so) is produced through the conical intersection dissociation pathway such that some of the OH product states lie above the $O ({}^{3}P) + H$ dissociation limit, which are supported only through large centrifugal barriers. The population distribution for $OH (X, v = 0)$ also shows an alternation with $N$ , similar to that observed for $H_{2} O$ that is attributed to dynamical interference. The tunneling rates of these extremely rotationally excited OH molecules are also analyzed.

Received 27 March 2001

DOI:https://doi.org/10.1103/PhysRevLett.87.253201

Authors & Affiliations

Steven A. Harich and Xuefeng Yang^*

Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan

Xueming Yang^†

Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan
and Department of Chemistry, National Tsing Hua University, Hsichu, Taiwan
and Dalian Institute of Chemical Physics, CAS, Dalian, China

Richard N. Dixon

School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom

^*Permanent address: Department of Chemistry, Dalian University of Technology, Dalian, China.
^†Corresponding author. Email address: xmyang@po.iams.sinica.edu.tw