  We study the existence, optimality, and construction of non-randomised
stopping times that solve the Skorokhod embedding problem (SEP) for Markov
processes which satisfy a duality assumption. These stopping times are hitting
times of space-time subsets, so-called Root barriers. Our main result is,
besides the existence and optimality, a potential-theoretic characterisation of
this Root barrier as a free boundary. If the generator of the Markov process is
sufficiently regular, this reduces to an obstacle PDE that has the Root barrier
as free boundary and thereby generalises previous results from one-dimensional
diffusions to Markov processes. However, our characterisation always applies
and allows, at least in principle, to compute the Root barrier by dynamic
programming, even when the well-posedness of the informally associated obstacle
PDE is not clear. Finally, we demonstrate the flexibility of our method by
replacing time by an additive functional in Root's construction. Already for
multi-dimensional Brownian motion this leads to new class of constructive
solutions of (SEP).
