The photoreaction of hydrogen clusters caused by cosmic-ray
irradiations
plays a crucial role in interstellar molecular clouds because the
reaction of molecules takes place in these surrounding clusters. Previous
gas-phase experiments introduced the reaction products after the ionization
of the neutral hydrogen cluster. In the experiments, the odd-numbered
hydrogen cluster cation, H+(H2)
m
, was the main product, while the even-numbered cluster
cation, (H2)
n
+,
was the minor product. However, the formation yield of (H2)
n
+ was significantly low.
Despite many theoretical calculations and experiments, the formation
mechanism of odd- and even-numbered cluster ions from ionized hydrogen
clusters is still unclear. In this study, the direct ab initio molecular
dynamics (AIMD) method was applied to the reaction of the hydrogen
cluster cation (H2)
n
+ to understand the abovementioned formation mechanism. The trajectories
of (H2)
n
+ following
the vertical ionization of the neutral cluster were calculated. Direct
AIMD calculations indicated that odd-numbered cluster cations, H3
+(H2)
n−2 + H (dissociation), were formed directly as the main product after
the ionization of (H2)
n
. An
even-numbered cluster, (H2)
n
+, was temporally formed when an H-shaped complex composed
of three H2 molecules existed within a neutral cluster.
However, it was rapidly dissociated to an odd-numbered cluster. Static
ab initio calculations suggested that the odd-numbered cluster complex,
H3
+(H2)
n−2-H, could be transferred to even-numbered ions via a transition state
with a low energy barrier. The even-numbered cluster cation was formed
stepwise from the odd-numbered cluster cation. The formation mechanism
of odd- and even-numbered cluster cations is discussed based on these
results.