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This paper proves that the computational power of quantum interactive proof systems, with a double-exponentially small gap in acceptance probability between the completeness and soundness cases, is precisely characterized by EXP, the class of problems solvable in exponential time by deterministic Turing machines. This fact, and our proof of it, has implications concerning quantum and classical interactive proof systems in the setting of unbounded error that include the following: • Quantum interactive proof systems are strictly more powerful than their classical counterparts in the unbounded-error setting unless PSPACE = EXP, as even unbounded error classical interactive proof systems can be simulated in PSPACE. • The recent proof of Jain, Ji, Upadhyay, and Watrous (STOC 2010) establishing QIP = PSPACE relies heavily on the fact that the quantum interactive proof systems defining the class QIP have bounded error. Our result implies that some nontrivial assumption on the error bounds for quantum interactive proofs is unavoidable to establish this result (unless PSPACE = EXP). • To prove our result, we give a quantum interactive proof system for EXP with perfect completeness and soundness error 1--2-2poly, for which the soundness error bound is provably tight. This establishes another respect in which quantum and classical interactive proof systems differ, because such a bound cannot hold for any classical interactive proof system: distinct acceptance probabilities for classical interactive proof systems must be separated by a gap that is at least (single-)exponentially small. We also study the computational power of a few other related unbounded-error complexity classes.