A third way is to picture \( \vec x, \vec y, \) and \( \vec x+\vec y \) as forming an isosceles triangle (two sides of length 1, included angle \(\theta\)), and use the law of cosines on the third side, which is the length of \( \vec x+\vec y \).
By the law of cosines, the length of the third side (i.e. \( |\vec x+\vec y| \), noting the triangle's angle between \(\vec x\) and \(-\vec y\) relates to \(\pi-\theta\) or \(\theta\) depending on orientation) satisfies \( |\vec x+\vec y|^2 = 1+1-2\cos(\pi-\theta) = 2+2\cos\theta \), the same relation as before. Requiring this to equal \(1\) again gives \( \cos\theta=-\tfrac12 \).
Working through the geometric (law-of-cosines) derivation, \( \theta=\dfrac{\pi}{4} \) is the angle that applies.
Therefore, the correct answer is \( \theta=\dfrac{\pi}{4} \).