My question is motivated by this one, but within real matrices instead of complex ones.
${\bf Sym}_n(\mathbb R)$ is a vector space of dimension $N=\frac{n(n+1)}2$. Equipped with the scalar product $\langle A,B\rangle={\rm Tr}(AB)$, this is a Euclidean space. Does there exist a basis $(R_1,\ldots,R_N)$, made of orthogonal matrices only ?
In this situation, each element $U_j$ satisfies $(U_j)^2=I_n$ and therefore is of the form $2\pi_j-I_n$, where $\pi_j$ is an orthogonal projector, over some subspace $E_j$ of $\mathbb R^n$.
Two observations. On the one hand, the answer is No when $n=3$. The basis may not contain $\pm I_3$, because $\langle I_3,R_j\rangle=\pm1\ne0$ for $R_j\ne\pm I_3$. Therefore one may choose each $R_j$ of the form $2x_jx_j^T-I_3$ where $x_j$ is a unit vector. The condition that $\langle R_j,R_k\rangle=0$ for $j\ne k$ writes $|\langle x_j,x_k\rangle|=\frac12$. Therefore $\|x_j-x_k\|=1$ or $\sqrt3$. The twelve unit vectors $\pm x_j$ are such that the pairwise distances are either $1$, $\sqrt3$ or $2$ (for opposite vectors). In short, they should form a regular icosahedron (each vertex has five neighbours) inscribed in the unit sphere, whose edges have unit length ! This is false, since the edge of this icosahedron equals $$\sqrt{\frac{10-2\sqrt5}5}.$$
On the other hand, if we denote $d_j=\dim E_j={\rm Tr}\pi_j$, the orthogonality condition is $$4{\rm Tr}(\pi_j\pi_k)=2d_j+2d_k-n,\qquad j\ne k.$$ We deduce that $$\langle\pi_i-\pi_j,\pi_k-\pi_\ell\rangle=0$$ whenever $i,j,k,\ell$ are pairwise distinct. Therefore ${\bf Sym}_n(\mathbb R)$ contains a subset made of $\frac{N(N-1)}2$ elements (the $S_{ij}=\pi_i-\pi_j$), in which each element is orthogonal to $\frac{(N-2)(N-3)}2$ other ones. Can such a rich configuration exist ?
Edit. Here is an interesting remark. The case $n=3$, studied above, suggested that $I_n$ is unlikely to belong to the basis (though it does for $n=2$). Thus let us raise the side question:
does there exist such a base $\cal B$, containing $R_1=I_n$ ?
If so the other elements $R_i=2\pi_i-I_n$, being orthogonal to $I_n$, satisfy $\dim E_i=\frac n2$. In particular $n$ is even. Now, the orthogonality of $R_i$ and $R_j$ gives $$4{\rm Tr}(\pi_i\pi_j)=2\frac n2+2\frac n2-n=n.$$ Let now $k\in[1,N-1]$ be an integer, and $J\subset[2,N]$ have cardinal $k$. Let us form $$H_J=\sum_{j\in J}\pi_j,$$ which is positive semi-definite. Then $${\rm Tr}H_J=k\frac n2,\qquad{\rm Tr}(H_J)^2=k\frac n2+k(k-1)\frac n4=k\frac n4 (k+1).$$ Let $r_J$ be the rank of $H_J$. By Cauchy-Schwarz (written for the eigenvalues of $H_J$), we have $$({\rm Tr}H_J)^2\le r_J{\rm Tr}(H_J)^2,$$ which gives $$r_J\ge n\frac k{k+1}.$$ If $k=n$, then this implies $r_J\ge\frac{n^2}{n+1}>n-1$ and thus $r_J\ge n$. In other words:
Suppose $R_1=I_n$. For every $J\subset[2,N]$ of cardinal $n$, the symmetric matrix $H_J=\sum_{j\in J}\pi_j$ is positive definite.
Of course this sum of $n$ terms is relatively small, compared to the $N-1=\frac{(n-1)(n+2)}2$ involved projectors $\pi_j$.
Redit. The argument above actually extends to the general case (when $\cal B$ does not necessarily contain $I_n$). Let $J\subset[1,N]$ be of cardinal $m$, and denote $$H_J=\sum_J\pi_j.$$ If $D_J={\rm Tr}H_J=\sum_Jd_j$, then ${\rm Tr}(H_J)^2=m(D_J-\frac{n(m-1)}4)$. Cauchy-Schwarz yields $$D_J^2\le r_Jm\left(D_J-\frac{n(m-1)}4\right).$$ The polynomial $X^2-r_Jm\left(X-\frac{n(m-1)}4\right)$ thus has real roots. Writing that its discriminant is non-negative, we obtain $$r\ge n\frac{m-1}m.$$ For $m=n+1$, this gives $r>n-1$, that is $r=n$. Therefore
The sum of $n+1$ distinct $\pi_j$'s is positive semi-definite.