We show that for a quantum system coupled to both vibrational and electromagnetic environments, enforcing additivity of their combined influences results in non-equilibrium dynamics that does not respect the Franck-Condon principle. We overcome this shortcoming by employing a collective coordinate representation of the vibrational environment, which permits the derivation of a non-additive master equation. When applied to a two-level emitter our treatment predicts decreasing photon emission rates with increasing vibrational coupling, consistent with Franck-Condon physics. In contrast, the additive approximation predicts the emission rate to be completely insensitive to vibrations. We find that non-additivity also plays a key role in the stationary non-equilibrium model behaviour, enabling two-level population inversion under incoherent electromagnetic excitation.
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