A quantum mechanical model of the ammonia predissociation dynamics is
presented. The effects of an excited state barrier and well, a deep co
nical intersection between the ground and excited states, and strong a
ngular dependence of the potential energy surfaces are explored. The p
redissociation rate is sensitive to both the vibrational (v(2)') and t
he rotational (J',K') level of the initially excited metastable state.
The product state distribution following excitation within the v(2)'
= 0 band reflects the shape of the ground bend resonance and is broad,
extending to the energetic limit. The photofragment angular distribut
ions following excitation of magnetic-rovibronic state-selected parent
molecules depend sensitively on the photon frequency. Their structure
varies markedly with the internal state of the accompanying NH, fragm
ent, The results are traced to the complex excitation dynamics, which
prepare a frequency-dependent superposition of rotational states, and
to the strong forces exerted on the dissociating system in the region
of the conical intersection.