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If $f$ is an irreducible polynomial, any two roots $\alpha ,\beta$ have the same minimal polynomial. Thus the map $\mathbb{Q}(\alpha )\to \mathbb{Q}(\beta )$ carrying $\alpha$ to $\beta$ is a field embedding. The extension theorem for field embeddings extends it to an embedding of the splitting field $L$ into an algebraic closure. Since $L/\mathbb{Q}$ is normal, its image is $L$, so it is an element of the Galois group.

Conversely, factor $f$ into irreducible factors over $\mathbb{Q}$. An automorphism preserves the vanishing of each factor, so it cannot send a root of one factor to a root of another. Since there are no repeated roots, different factors have disjoint root sets. Transitivity on all roots therefore forces a single irreducible factor. This proves the equivalence.