The effect of parent zero-point motion on the ND2 ((A)over-tilde) rotational state distribution in the 193.3 nm photolysis of ND3

The vibrational and rotational product-state distributions of ND2((A) over tilde (2)A(1)) has been probed following the photodissociation of ND3 at 193.3 nm by time-resolved Fourier Transform infrared emission spectroscopy. The dynamics of the bond cleavage are inferred from the product state distributions by comparison with an earlier study of the photodissociation of NH3. The degree of excitation about the minor rotational b/c-axes of the product is attributed to the amount of zero-point energy of the parent molecule in the v(4), H-N-H (D-N-D) scissors bending coordinate of the NH3/ND3((A) over tilde) predissociative state. A bimodal ND2((A) over tilde(2)A(1)) distribution is observed for rotation about the primary a-axis, analogous to the NH, fragment formed in the photodissociation of NH3. (C) 2000 Elsevier Science B.V. All rights reserved.