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The STM induced rotation and dissociation dynamics of a single oxygen
molecule on the Pt(111) surface have been finally determined by first
principles calculations together with a newly developed statistical model for
inelastic electron tunneling. Several long-standing puzzles associated with
these dynamic processes in this classic system have been fully resolved. It is
found that the unexpected low energy barrier of the O2 rotation is originated
from an ingenious pathway, while the prior occupation of the metastable
hcp-hollow site after the O2 dissociation can be attributed to a dynamic
process of surface accommodation. The experimentally observed non-integer
power-law dependence of the rotation rate as a function of the current can be
perfectly explained by taking into account the randomness of multi-electron
inelastic tunneling processes.