I will prove the claim from Jaap's comment. As a consequence, we can deduce that all eigenvalues of $P_n$ will be of the form $\exp(2 \pi i \cdot k/m)$, where $m$ is the order of $2$ modulo $n$. That said, we don't necessarily know what the multiplicity of these eigenvalues will be.
Claim: The length of the longest cycle is the multiplicative order of $2$ mod $n$. The other cycle lengths divide that.
Proof: First, let $k$ denote the smallest positive integer for which $P_n^k = I$. Let $m$ denote the order of $2$ modulo $n$. I claim that $k = m$.
To see this, note that $P_n^m = I$ (why?). It follows that $k \mid m$ (why?). Conversely, the fact that $P_n^k = I$ means that $2^k \cdot i \equiv i \pmod n$ for all $i$. Since this holds for $i=1$, we see that $2^k \equiv 1 \pmod n$. Conclude that $m \mid k$. With that, we have $m = k$ as desired.
Now, decompose the permutation associated with $P_n$ into disjoint cycles. The fact that $P_n^m = I$ means that each cycle has an order that divides $m$. On the other hand, we see from the above claim that $m$ is the length of the cycle containing $i = 1$. So indeed, $m$ is the length of the longest cycle and the length of each cycle divides $m$.
Further observations of interest:
- There will always be a cycle $(0)$ and associated eigenvalue $1$.
- By Euler's theorem, we will always have $m \mid \varphi(n)$, where $\varphi$ denotes Euler's totient function.
- For an arbitrary $i$, we have
$$
2^k i \equiv i \pmod n \iff
n \mid (2^k - 1)i
$$
Why $P_n^m = I$: note that $P_n^j$ is the matrix where the column position of $1$ in the $i$th row is $2^j \cdot i \pmod n$. The fact that $2^m = 1$ means that $P_n^m$ has a $1$ in the $i$th position of the $i$th row for each $i$, which is to say that $P_n^m$ is the identity matrix.
Why $k \mid m$: suppose to the contrary that $k \nmid m$. Write $m = q\cdot k + r$ (for some integers $q,r$ with $0< r < k$). We note that
$$
P_n^r = P_n^{m - q \cdot k} = P_n^m \cdot (P_n^{k})^{-q} = I \cdot I = I,
$$
contradicting our definition of $k$ as the smallest positive integer for which $P_n^k = I$