To account for these higher-energy geometries, the spectral library can be searched with an energy tolerance, where the ranking is based on the best matching computed spectrum per entry. For a tolerance of 10 kJ/mol, this results in an overall better performance as derived from the RP, which improves from 18.2 to 17.0 in the unsupervised search. However, the 10 kJ/mol tolerance increases the number of considered spectra about 3-fold (to 10811 on average), possibly leading to a worse ranking for metabolites that already performed well. This effect becomes pronounced when all adductconstrained spectra in the in silico library are searched, i.e. without energy constraints (24865 spectra on average, Table ), yielding a poorer RP of 19.0.