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Yemon Choi
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By means of singular value decomposition, I think that the general answer for a real n by n matrix should be: Required volume = $$ {\rm vol}(O(n))^2 \int\limits_{0\leq s_n \leq s_{n-1}\leq \dots s_1\leq 1}\prod_{i < j < n} (s_ i^2-s_ j^2).$$

O(n) is the n-dimensional orthogonal group