Abstract

An anisotropic spatial velocity distribution was observed for NO⁺ produced following one-color photolysis/ionization of tert-butyl nitrite (TBN) by a pulsed polarized laser at 266, 355 and 532 nm in a time-of-flight mass spectrometer. The dependence of the NO⁺ fragment mass peak profile on the wavelength and on the polarization was monitored. The most striking feature is the varying fragment peak splitting obtained under the same experimental conditions by changing the laser polarization direction. This phenomenon is a result of the vector correlation between the laser polarization,Ê, at a given wavelength, the electronic transition dipole moment of TBN,μ, and the direction of the NO fragment velocity, v. The dynamics of the photodissociation process and, in particular, its directional properties are discussed in view of these results.