We develop an approach to light-matter coupling in waveguide QED based upon scattering amplitudes evaluated via Dyson series. For optical states containing more than single photons, terms in this series become increasingly complex and we provide a diagrammatic recipe for their evaluation, which is capable of yielding analytic results. Our method fully specifies a combined emitter-optical state that permits investigation of light-matter entanglement generation protocols. We use our expressions to study two-photon scattering from a $Lambda$-system and find that the pole structure of the transition amplitude is dramatically altered as the two ground states are tuned from degeneracy.
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