We study the associated production of a charged Higgs and a W boson in high-energy pp collisions at the Large Hadron Collider. This is an interesting process for charged Higgs discovery, or exclusion, since the production cross section could depend strongly on the model, offering potential discriminating power between supersymmetric extensions of the Standard Model with minimal or extended Higgs sectors. We compute the cross section for this process in the next-to-minimal supersymmetric

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... Model (NMSSM), at the tree level for quark-quark scattering and at one-loop level for gluon-gluon scattering. The most important corrections beyond leading order are taken into account using an improved Born approximation. We find that the pp → H^± W^∓ cross section can be resonantly enhanced by up to an order of magnitude over its MSSM value (both for √(s)=7 TeV and 14 TeV) through the contributions of heavy, neutral, singlet-dominated Higgs bosons appearing in the s-channel. Since such Higgs mass configurations are normally not possible in the MSSM, the observation of associated H^± W^∓ production at the LHC could provide a striking, although indirect, signature of a more complicated Higgs sector.