I don't have a good reference, but I can work out the beginning of the answer for you. I will work just over mathbbC, and I will call my simple Lie algebra mathfrakg.
First, you must decide what you mean by "outer automorphism". We know what an automorphism is, and an "inner automorphism" should be conjugation by something. Of course, for xinmathfrakg, the bracket textadx=[x,−]inmathfrakgl(mathfrakg) is a derivation of mathfrakg, not an automorphism. So I assume you mean the automorphism exp(textadx)inrmGL(mathfrakg) as the inner automorphism. Now, the set of matrices of the form exp(textadx) is not a group, but generates a connected group, which I will call textInn(mathfrakg). (Remark: any automorphism of mathfrakg preserves the Killing form, so we really have textInn(mathfrakg)subseteqtextAut(mathfrakg)subseteqrmSO(mathfrakg).) Of course, mathfrakg acts on itself faithfully since it is simple, so textLiebigl(textInn(mathfrakg)bigr)=mathfrakg, but textInn(mathfrakg) may not be simply-connected. Regardless, it is a quotient of the connected simply-connected simple group G with Lie algebra mathfrakg, and so you could if you prefer consider inner automorphisms to be given by the adjoint action of G.
Now, over mathbbC (and this requires facts about the topology of mathbbC), any two choices of Cartan subalgebra are conjugate by an element of textInn(mathfrakg). See, for example, Proposition 5.32 of my notes on the class by M. Haiman. So, to understand textOut(mathfrakg)=textAut(mathfrakg)/textInn(mathfrakg), it suffices to understand how it acts any chosen Cartan subalgebra mathfrakh.
Any automorphism of mathfrakg that fixes mathfrakh must act on the root lattice, and must take some system of positive roots to some system of positive roots. Now, any two systems of positive roots are related by the Weyl group WsubseteqrmGL(mathfrakh∗). (Proposition 5.60 from my notes.) On the other hand, we have W=mathcalNG(H)/H, the normalizer of the maximal torus H=expmathfrakh in G modulo H, which acts trivially on mathfrakh. So W acts on mathfrakh by inner automorphisms, indeed by mathcalNG(H)subseteqG.
A system of positive roots picks out a Cartan matrix and corresponding Dynkin diagram, and conversely from this matrix you can reconstruct the group. Thus, the only possible source of outer automorphisms of come from automorphisms of the Dynkin diagram.
So your question follows simply from looking at the Dynkin diagrams. In particular, A1, the B and C series, and the exceptional groups G2,F4,E7,E8 have no outer automorphisms. For the others, you have to do a calculation. Maybe it's obvious, but it's late; I'll think about it. As others pointed out in the time I took to write this answer, the theorem is that automorphisms of the Dynkin diagram are all outer. Actually, perhaps this is obvious. If an automorphism of the Dynkin diagram were inner, then it would induce among other things an automorphism of H, and so be in the Weyl group, and you must convince yourself that non-trivial elements of the Weyl group do not preserve the system of positive roots. But this is essentially the statements that W acts faithfully on H and that each W-orbit intersects the positive Weyl chamber only once. So I am using the fact that W=mathcalNG(H)/H, which off the top of my head right now I don't know how to prove.
Notice that for semisimples, the Dynkin might be disconnected, and clearly any inner automorphism preserves the connected components. So there are certainly outer automorphism for mathfrakgtimesn given by the Sn that permutes the pieces.
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