We present a novel
approach to the generation of new crystalline
phases, which is based on a combination of the topological description
of crystal structures as a periodic net and the extended Zintl–Klemm
concept, which establishes the structural relations between chemically
and structurally simpler and more complex inorganic compounds. With
this approach, we have explored the structural similarities between
all known binary sulfides, selenides, and the corresponding simple
sulfates and selenates and have theoretically revealed seven new high-pressure
phases in the last two groups of compounds. Using density functional
theory methods, we have studied the thermodynamic and mechanical stability
of the new phases, have adjusted the transition pathways in the sulfate
and selenate systems, and have revealed new structural correlations
of the baric polymorphism in these systems. The advantages of the
topological approach compared to conventional methods of modeling
crystal structures are discussed and illustrated.