Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2009-04-23

Photodissociation dynamics of N-methylindole, N-methylpyrrole, and anisole.

Chien-Ming Tseng, Yuan T Lee, Chi-Kung Ni

Index: J. Phys. Chem. A 113(16) , 3881-5, (2009)

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Abstract

Photodissociation experiments employing molecular beams of N-methylindole, N-methylpyrrole, and anisole at 193 and 248 nm, respectively, have been conducted using multimass ion imaging techniques. We find that CH3 elimination is the sole dissociation channel for the studied molecules at both 193 and 248 nm. The photofragment translational energy distribution of anisole is found to contain both fast and slow components at the two wavelengths. On the other hand, a fast component (large recoil velocity) is dominant for N-methylindole at 248 nm, and a slow component (small recoil velocity) is dominant at 193 nm. The absorption coefficient of N-methylpyrrole is too weak for study at 248 nm. The photofragment translational energy distribution at 193 nm includes a large portion of the slow component and a small portion of the fast component. The findings indicate that the fast component corresponds to dissociation from the repulsive excited state and the slow component corresponding to dissociation from the ground electronic state. A comparison with the photodissociation dynamics of phenol, pyrrole, and indole suggests that replacement of the H atom by CH3 does not change the dissociation channels on the excited state. However, the respective dissociation channels for anisole and N-methylpyrrole on the ground state differ significantly from that for phenol and pyrrole.