Determination of all scattering phases and amplitudes in the photodissociation of a diatomic molecule

Andrew Orr-Ewing (1) , Oleg Vasyutinskii (2) , Andrey Smolin (2)

1 School of Chemistry
2 A.F. Ioffe Physical-Technical Institute

Analysis of the rank K=0-3 anisotropy (orientation and alignment) parameters describing the angular momentum polarization of the Cl(²P_3/2 atoms formed from the 467-nm photodissociation of BrCl enables the relative phases and the amplitudes of the nuclear wavefunctions to be obtained for all of the five adiabatic potential energy curves with Ω=0⁺ and 1 correlating to the lowest dissociation limit. A so-called "complete" experiment is thus demonstrated for photodissociation of this diatomic molecule in which all the components of the photofragmentation T-matrix are derived. Quantification of the amplitudes of dissociative flux on the X¹Σ⁺₀₊, A³Π₁, B³Π₀₊, C¹Π₁ and D(1) states demonstrates the importance of non-adiabaticity in the dissociation dynamics. The relative phases contain contributions arising from nuclear motion on potential energy curves of different shapes in the short-range region, and from dynamical phase shifts associated with non-adiabatic transitions.

Mots clés: Physical Sciences

Andrew Orr-Ewing, Oleg Vasyutinskii, Andrey Smolin. Determination of all scattering phases and amplitudes in the photodissociation of a diatomic molecule. Molecular Physics, 2007, 105 (05-07), pp.885-892. ⟨10.1080/00268970601063804⟩. ⟨hal-00513055⟩