14:48
Easiest way I know to proceed is to note that if $M=U^T U$ then for any column 3-vector $v$ one has $v^T M v = v^T U^T U v=\|U v\|^2\geq 0$. Hence $M$ will be positive semidefinite by definition ($v^T M v\geq 0$ for all $v$.)
But an equivalent condition for a matrix to be PSD is that all the principal minors be nonnegative. These minors here are the diagonal elements, the 2-by-2 principal minors e.g. $\begin{vmatrix} 1 & x \\ x & 1\end{vmatrix}=1-x^2$, and the determinant. The first are 1's and therefore positive, the second is nonnegative since they're cosines of angles, and all that remains is $\det M = 1+2xyz-x^2-y^2-z^2$. So $M$ is PSD iff $\det M\geq 0$ with $(x,y,z)\in[-1,1]^3$.
Writing $f(x,y,z)=\det M$, you can check that $f(0,0,0)=1$, $f(1,1,1)=0$, and $f(1,1,-1)=-4$. So (1,1,-1) is not in the set of allowed cosines, (1,1,1) is on the boundary of said set, and (0,0,0) is inside the set.
As a special case, when $z=1$ one has $f(x,y,1)=2xy-x^2-y^2=-(x-y)^2$ which is nonnegative when $x=y$ i.e. the line segment $(x,y,z)=(t,t,1)$ with $t\in[-1,1]$ satisfies $f=0$.
That connects the corners $(1,1,1)$ and $(-1,-1,1)$. There will be five other such line segments which run between the four allowed vertices.
And by convexity of PSD matrices one concludes that the tetrahedron generated by the four allowed vertices is definitely in the set. So a natural question is whether there's any points outside of it.
and the answer turns out to be yes: for instance, the point $(-1/2,-1/2,-1/2)$ will be outside.