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We give a method for computing asymptotic formulas and approximations for the volumes of spectrahedra, based on the maximum-entropy principle from statistical physics. The method gives an approximate volume formula based on a single convex optimization problem of minimizing $-\log \det P$ over the spectrahedron. Spectrahedra can be described as affine slices of the convex cone of positive semi-definite (PSD) matrices, and the method yields efficient deterministic approximation algorithms and asymptotic formulas whenever the number of affine constraints is sufficiently dominated by the dimension of the PSD cone. Our approach is inspired by the work of Barvinok and Hartigan who used an analogous framework for approximately computing volumes of polytopes. Spectrahedra, however, possess a remarkable feature not shared by polytopes, a new fact that we also prove: central sections of the set of density matrices (the quantum version of the simplex) all have asymptotically the same volume. This allows for very general approximation algorithms, which apply to large classes of naturally occurring spectrahedra. We give two main applications of this method. First, we apply this method to what we call the "multi-way Birkhoff spectrahedron" and obtain an explicit asymptotic formula for its volume. This spectrahedron is the set of quantum states with maximal entanglement (i.e., the quantum states having univariant quantum marginals equal to the identity matrix) and is the quantum analog of the multi-way Birkhoff polytope. Second, we apply this method to explicitly compute the asymptotic volume of central sections of the set of density matrices.