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A combination of steady\u2010state IR and UV cryogenic ion spectroscopies with picosecond pump\u2010probe photodissociation experiments sheds new lights on the deactivation processes of TrpH<jats:sup>+<\/jats:sup> and conformer\u2010selected TrpH<jats:sup>+<\/jats:sup>\u2212H<jats:sub>2<\/jats:sub>O complex, supported by quantum chemistry calculations at the DFT and coupled\u2010cluster levels for the ground and excited states, respectively. TrpH<jats:sup>+<\/jats:sup> excited at the band origin exhibits a transient of less than 100\u2005ps, assigned to the lifetime of the excited state proton transfer (ESPT) structure. The two experimentally observed conformers of TrpH<jats:sup>+<\/jats:sup>\u2212H<jats:sub>2<\/jats:sub>O have been assigned. 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