This work shows how the N 1s photoemission (PE) spectrum of self-associated melamine molecules in aqueous solution has been successfully rationalized using an integrated computational approach encompassing classical metadynamics simulations and quantum calculations based on density functional theory (DFT). The first approach allowed us to describe interacting melamine molecules in explicit waters and to identify dimeric configurations based on pi-pi and/or H-bonding interactions. Then, N 1s binding energies (BEs) and PE spectra were computed at the DFT level for all structures both in the gas phase and in an implicit solvent. While pure pi-stacked dimer s show gas-phase PE spectra almost identical to that of the monomer, those of the H-bonded dimers are sensibly affected by NH center dot center dot center dot NH or NH center dot center dot center dot NC interactions. Interestingly, the solvation suppresses all of the non-equivalences due to the H-bonds yielding simila r PE spectra for all dimer s , matching very well our measurements.
