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First of all, note that $\pi:X\rightarrow Y$ bijective is not enough to conclude that $\pi$ is an isomorphism. For instance consider $C\subset\mathbb{A}^2$ a cubic with a cusp and let $\pi:\mathbb{A}^1\rightarrow C$ given by $t\mapsto (t^2,t^3)$. Then $\pi$ is bijective, it is indeed a topological homomorphism. However, $C$ is singular and $\mathbb{A}^1$ is smooth. Therefore $\pi$ can not be an isomorphism. As you see the differential $d\pi_{0}$ of $\pi$ in zero is zero.

Let $\pi:X\rightarrow Y$ be a morphism or relative dimension $r$ of smooth varieties over an algebraically closed field. Assume that the relative cotangent sheaf $\Omega_{X/Y}$ is locally free of rank $r$ on $X$. We have an exact sequence $$\pi^{*}\Omega_{Y}\rightarrow\Omega_{X}\rightarrow\Omega_{X/Y}\mapsto 0.$$ Let $k(x)$ be the residue field at a closed point $x$. Tensorizing we get
$$\pi^{*}\Omega_{Y}\otimes k(x)\rightarrow\Omega_{X}\otimes k(x)\rightarrow\Omega_{X/Y}\otimes k(x)\mapsto 0.$$ Since $X$ and $Y$ are smooth and $\Omega_{X/Y}$ is locally free of rank $r$ these three vector spaces are of dimension $dim(Y),dim(X),r$ respectively. So the first map is injective and we have $$0\mapsto\pi^{*}\Omega_{Y}\otimes k(x)\rightarrow\Omega_{X}\otimes k(x)\rightarrow\Omega_{X/Y}\otimes k(x)\mapsto 0.$$ For any closed point $x\in X$ we have $k(x)\cong k$. Therefore we can identify the injective map $\pi^{*}\Omega_{Y}\otimes k\rightarrow\Omega_{X}\otimes k$ with the map between the cotangent spaces $\mathfrak{m}_y/\mathfrak{m}^2_y\rightarrow\mathfrak{m}_x/\mathfrak{m}^2_x$ where $y = \pi(x)$. Dualizing we have that the differential $T_\pi(x):T_xX\rightarrow T_yY$ is surjective. Therefore $\pi$ is a smooth morphism.

In particular, if any fiber of $\pi$ is just one point, then $\Omega_{X/Y}$ is locally free of rank $r = 0$ and $\pi$ is a smooth morphism of relative dimension zero. Finally, since $\pi$ is surjective it is an isomorphism.

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