Is it true that we can define a field as a group $G$ that is isomorphic to its automorphism group?
I believe it's an equivalent definition if addition is the group operation of $G$ and multiplication is the application of the automorphism corresponding to the left element to the right element.
No, this is wrong for a whole bunch of reasons. If $F$ is a field, there is a map from the set of nonzero elements of $F$ to the group of automorphisms of the additive group $(F,+)$. However, this does not mean that $(F,+)$ is isomorphic to its own automorphism group, for quite a lot of different reasons:
(And this is not even getting into the issues you would have going "the other way", starting with a group isomorphic to its automorphism group and getting a field. For instance, such a group need not be abelian.)