Q1. Why does Time Hierarchy prove P ⊊ EXPTIME but not PSPACE ⊊ EXPTIME?
Time Hierarchy compares time-bounded classes within the same model. P uses polynomial time; EXPTIME uses exponential time; the hierarchy theorem gives the strict separation. PSPACE uses polynomial space — a different resource. Comparing PSPACE to EXPTIME requires bridging time and space, which the hierarchy theorem doesn't do.
Q2. Is PSPACE = EXPTIME possible?
Currently can't be ruled out. Most experts believe PSPACE ⊊ EXPTIME (exponential time should be much larger than polynomial space), but no proof exists. Relativised oracle separations exist but don't transfer.
Q3. What's the relationship to P vs NP?
The chain is P ⊆ NP ⊆ PSPACE ⊆ EXPTIME, with P ⊊ EXPTIME being the only proven strict containment. So at least one of the three middle inclusions must be strict, but we don't know which.
Q4. What does the sandwich theorem tell us?
SPACE(f) ⊆ TIME(2O(f)) gives PSPACE ⊆ EXPTIME. The reverse inclusion (EXPTIME ⊆ PSPACE?) isn't known and is widely conjectured false.