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Molecular orientation is a fundamental requisite in the study ofstereodirected dynamics of collisional and photoinitiated processes. In thislast decade, variable hexapolar electric filters have been developed andemployed for the rotational-state selection and the alignment of molecules ofincreasing complexity, for which main difficulties are their mass, their lowsymmetry and the very dense rotational manifold. In this work, for the firsttime, a complex molecule such as 2-bromobutane, an asymmetric-top containing aheavy atom (the bromine), has been successfully oriented by a weak homogeneousfield placed downstream the hexapolar filter. Efficiency of the orientation hasbeen characterized experimentally, by combining time-of-flight measurements anda slice-ion-imaging detection technique. The application is described to thephotodissociation dynamics of the oriented 2-bromobutane, which was carried outat a laser wavelength of 234 nm, corresponding to the breaking of the C Brbond. The Br photofragment is produced in both the ground Br (2P3/2) and theexcited Br (2P1/2) electronic states and both channels are studied by the sliceimaging technique, revealing new features in the velocity and angulardistributions with respect to previous investigations on non-orientedmolecules.

Hexapole-Oriented Asymmetric-Top Molecules and Their Stereodirectional Photodissociation Dynamics