Quantum dynamics of the Br2 (B-excited state) photodissociation in superfluid helium nanodroplets: importance of the recombination process

Abstract

We have studied the Br₂ photodissociation dynamics (B ← X electronic transition) of Br₂(v = 0, X)@(⁴He)_N doped nanodroplets (T = 0.37 K) at zero angular momentum, with N in the 100–1000 interval. To do this, we have used a quantum mechanical hybrid strategy proposed by us and, as far as we know, this is the second quantum dynamics study available on the photodissociation of molecules in superfluid helium nanodroplets. While the results obtained for some properties are qualitatively similar to those reported previously by us for the Cl₂(B ← X) related case (in particular, the oscillating Br final velocity distribution which also arises from quantum interferences), large differences are evident in three key properties: the photodissociation mechanism and probability and the time scale of the process. This can be interpreted on the basis of the significantly lower excitation energy achieved by the Br₂(B ← X) transition and the higher reduced mass of Br–Br in comparison to the chlorine case. The Br₂(B) photodissociation dynamics is significantly more complex than that of Cl₂(B) and leads to the fragmentation of the initial wave packet. Thus, the probability of non-dissociation is equal to 17, 18, 51, 85 and 100% for N = 100, 200, 300, 500 and 1000, respectively, while for chlorine this probability is equal to zero. In spite of the very large experimental difficulties that exist for obtaining nanodroplets with a well defined size, we hope that these results will encourage experimentalists to investigate these interesting systems.