Using the change of variable $k=n+1-i$ and some simple algebraic manipulations, one sees that the $n$th sum $S_n$ is
$$
S_n=\frac1{\sqrt{n}}\frac{n!}{n^n}\sum_{i=0}^{n-1}\frac{n^i}{i!}=\frac1{\sqrt{n}}\frac{n!}{n^n}\mathrm e^n\mathbb P(Z_n\leqslant n-1),
$$
where $Z_n$ is a random variable with Poisson distribution of parameter $n$. Thus, $Z_n$ is distributed as $Y_1+\cdots+Y_n$, where the sequence $(Y_n)_{n\geqslant1}$ is i.i.d. with Poisson distribution of parameter $1$. The central limit theorem applied to the sequence $(Y_n)_{n\geqslant1}$ shows that $T_n=(Z_n-n)/\sqrt{n}$ is asymptotically standard normal when $n\to\infty$, and in particular,
$$
\mathbb P(Z_n\leqslant n-1)=1-\mathbb P(T_n\geqslant0)\to1-\tfrac12=\tfrac12.
$$
This asymptotics, together with Stirling's approximation formula $n!\sim\sqrt{2\pi n}(n/\mathrm e)^n$, implies that $S_n\to\sqrt{\pi/2}$ when $n\to\infty$.