I agree that the algebra implies a bijection. But, geometrically
the space of correlation matrices is a cone (think in terms of
the eigenvalues — they’re constrained to lie on a circle for any
given value of the determinant, and as the the value of the
determinant shrinks that circle shrinks until it collapses to a point
when at least one of the eigenvalue vanishes.
Now if we ignore singularities then we have a cone minus that
endpoint, which is a cylinder. So the space of non-singular
correlation matrices should be a cylinder, which is not equivalent
to a patch of R^{choose(n , 2)} for the same reason the circle
isn’t (the identification of the endpoints can’t be matched in
a Euclidean space). I’ve attached a figure demonstrating how
we need at least two parameterizations (charts) to cover the
cylinder.
So geometrically there should be at least one line of points
in correlation matrix space that can’t be identified using the
single algebraic transformation. Hence the tension.