Hemiquantal time dependent calculation of the absorption spectrum of a photodissociating triatomic

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Abstract
A half-collision process is described within a hemiquantal time dependent model to calculate the absorption line shape. The photodissociation of ICN in a collinear geometry serves as an illustrative example with the ‘‘light’’ CN motion treated quantum mechanically, whereas the ‘‘heavy’’ I–CN motion is treated classically. The emphasis is put on (i) the way to introduce the Wigner distribution which appears to be the equivalent of the classical density matrix, and (ii) the choice of the initial positions and momenta in the sampling of trajectories. The so-obtained converged results compare, within good accuracy, with the full quantal ones. Both conceptually and computationally, the hemiquantal approach appears as an interesting alternative to the full quantum wave packet calculation.