Reflections over a plane.

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Suppose $E$ is a three-dimensional Euclidean vector space. The reflection plane $F$ through the origin can be defined by a vector $v$ which is orthogonal to the plane. The reflection of a point $x$ about this plane is the linear isometry of $E$. $$s_Fx = x-2\frac{\langle v,x \rangle}{|v|^2}v$$ Now I want to show that $-s_F$ is the reflection in a line orthogonal to that plane, or similarly the rotation of $180^\circ$ around that axis.

I can easily do this if $F$ is the plane orthogonal to a base vector of E. Since then for a unit vector $e_i$ orthogonal to $F$ and belonging to the basis of E: $s_Fx = x - 2\langle e_i, x \rangle e_i = x-2x_i$ and thus $-s_Fx = -x + 2x_i$. And thus the different kind of reflections can be easily shown.

Now I was wondering if I could choose a similar approach to an arbitrary $F$ one that isn't necessarily orthogonal to one of the base vectors of $E$. I guess taking any change of basis to a basis triple including the the orthogonal vector could let me give a similar argument.

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Yes, you are free to change to another orthonormal basis with $f_1,f_2\in F$.

Geometrically, observe that $x\mapsto -x$ is the composition of reflections through the planes $(e_1,e_2),\ (e_1,e_3),\ (e_2,e_3)$ (in any order) for any orthogonal basis $e_1,e_2,e_3$, and the composition of any two of these is the reflection through their intersection.

Thus, with the basis $f_1,f_2,f_3$ above, we get $$-s_F=\left(s_{(f_2,f_3)}\circ s_{(f_1,f_3)}\circ s_{(f_1,f_2)}\right)\circ s_F=s_{(f_2,f_3)}\circ s_{(f_1,f_3)}=s_{f_3}\,. $$

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If I understand well, you are looking for a matrix expression for an "oblique" symmetry wrt to the given plane (with basis $x_1,x_2$) parallel to the given vector $x_3$ (pictured in red on the following figure), this vector being in general non normal to the plane.

enter image description here

We know that the orthogonal reflection with respect to horizontal plane $xOy$ is

$$S=\begin{pmatrix}1&0&0\\0&1&0\\0&0&-1\end{pmatrix}$$

Now, let us "adapt" this transformation to the new base $x_1,x_2,x_3$. More explicitly, let us define :

$$B=[x_1|x_2|x_3]$$

where the $x_i$s are here meant as the coordinates of vectors $x_i$ wrt to the canonical basis.

The looked for oblique symmetry matrix is therefore merely a change of basis operation :

$$S=BSB^{-1}$$

Otherwise said, the eigenvalue-eigenvector decomposition of the symmetry matrix...