I'll use 3-D coordinates with the $z$-axis passing through the poles, so we start at $(\cos \theta, 0, \sin \theta)$$\alpha:=(\cos \theta, 0, \sin \theta)$. The optimal path $\gamma$ must be a geodesic, so $\gamma$ is an arc of a great circle through $(\cos \theta, 0, \sin \theta)$$\alpha$. Let $\nu$ be a vector in $\mathbb{R}^3$ othogonalorthogonal to $\gamma$. Since $(\cos \theta, 0, \sin \theta) \in \gamma$$\alpha \in \gamma$, we have $(\cos \theta, 0, \sin \theta) \cdot \nu = 0$$\alpha \cdot \nu = 0$.
Let the end point of this geodesic have longitude $\psi$. Then $\gamma$ must be the shortest path to the line of longitude $(-\sin \psi, \cos \psi, 0)^{\perp}$. Set $\lambda := (-\sin \psi, \cos \psi, 0)$. So $\gamma$$\gamma=\nu^{\perp}$ and $(-\sin \psi, \cos \psi, 0)^{\perp}$$\lambda^{\perp}$ must meet orthogonally, which means that $(-\sin \psi, \cos \psi, 0) \cdot \nu = 0$$\lambda \cdot \nu = 0$.
So $\nu$ is a multiple of $$(\cos \theta, 0, \sin \theta) \times (-\sin \psi, \cos \psi, 0) = (-\cos (\psi) \sin (\theta),-\sin (\psi) \sin (\theta),\cos (\psi) \cos (\theta )).$$$$\alpha \times \lambda = (-\cos (\psi) \sin (\theta),-\sin (\psi) \sin (\theta),\cos (\psi) \cos (\theta )).$$
The point of intersection of the geodesic $\nu^{\perp}$ with the line of longitude $(-\sin \psi, \cos \psi, 0)^{\perp}$$\lambda^{\perp}$ is a scalar multiple of $$(-\sin \psi, \cos \psi, 0) \times \nu= (\cos ^2(\psi) \cos (\theta),\sin (\psi) \cos (\psi) \cos (\theta),\sin (\theta)).$$
One can compute$$\lambda \times \nu=-(\lambda \times (\lambda \times \alpha))=(\cos ^2(\psi) \cos (\theta),\sin (\psi) \cos (\psi) \cos (\theta),\sin (\theta)).$$ Now, taking the angle betweencross product with $(\cos \theta, 0, \sin \theta)$ and$\lambda$ twice is just $(\cos ^2(\psi) \cos (\theta),\sin (\psi) \cos (\psi) \cos (\theta),\sin (\theta))$ in order(up to find out how long the path isscalar) orthogonal projection onto $\lambda^{\perp}$, so we can write this more simply as $\alpha - \langle \lambda, \alpha \rangle \lambda$. I getAnd the answer thatangle between $\alpha$ and the lengthorthogonal projection of the path$\alpha$ onto $\lambda^{\perp}$ is $$\sin^{-1}(\cos \theta \sin \phi).$$ That's simple enough $\sin^{-1} (\alpha \cdot \lambda)$ (using that there$\alpha$ and $\lambda$ are both unit vectors), which is probably a better derivation; I just slogged through trig identities to get it. $$\sin^{-1} {\big(} (\sin \phi) (\cos \theta) {\big)}.$$