A first principles treatment of the photodissociation of HCl and DCl from 50000 cm1 to 75000 cm1 is
presented. The treatment is the first to correctly reproduce the asymmetric absorption profile observed
for HCl. The theoretical model for the HCl and DCl photodissociation presented in this study considers a
dissociation process that occurs on a repulsive electronic state (A1P) coupled to a bound electronic state
(C1P). The asymmetry in the HCl cross section arises because of the radial coupling introduced by the
rotation-free nuclear kinetic energy operator.