Photodissociation dynamics of the phenyl radical via photofragment translational spectroscopy

作者：Negru Bogdan; Goncher Scott J; Brunsvold Amy L; Just Gabriel M P; Park Dayoung; Neumark Daniel M^*

来源：Journal of Chemical Physics, 2010, 133(7): 074302.

DOI：10.1063/1.3473743

• nonlinear optical susceptibility
• particle interferometry
• vibration control

Photofragment translational spectroscopy was used to study the photodissociation dynamics of the phenyl radical C(6)H(5) at 248 and 193 nm. At 248 nm, the only dissociation products observed were from H atom loss, attributed primarily to H+o-C(6)H(4) (ortho-benzyne). The observed translational energy distribution was consistent with statistical decay on the ground state surface. At 193 nm, dissociation to H+C(6)H(4) and C(4)H(3)+C(2)H(2) was observed. The C(6)H(4) fragment can be either o-C(6)H(4) or l-C(6)H(4) resulting from decyclization of the phenyl ring. The C(4)H(3)+C(2)H(2) products dominate over the two H loss channels. Attempts to reproduce the observed branching ratio by assuming ground state dynamics were unsuccessful. However, these calculations assumed that the C(4)H(3) fragment was n-C(4)H(3), and better agreement would be expected if the lower energy i-C(4)H(3)+C(2)H(2) channel were included.

• 出版日期2010-8-21