Vibrational Predissociation Spectroscopy of Cold Protonated Tryptophan with Different Messenger Tags

Vibrational spectra of protonated tryptophan were recorded by predissociation of H2 messenger tags using cryogenic ion traps. We explore the issue of messenger induced spectral changes by solvating TrpH+(H2)n with n = 1–5 to obtain single photon vibrational spectra of TrpH+ and of its partly deuterated isotopomer in the spectral region of 800–4400 cm–1. Depending on the number of messenger molecules, the spectra of several conformational isomers associated with multiple H2 binding locations along with two natural conformations of TrpH+ were found using the two photon MS3IR2 conformational hole burning method. Most probable messenger positions were established by comparison with predictions from DFT calculations on various candidate structures. Mechanical anharmonicity effects associated with the charged amino group were modeled by Born–Oppenheimer ab initio molecular dynamics. The spectra of TrpH+(H2O)m=1,2, recorded by infrared multiphoton dissociation (IRMPD), reveal broad features in the NH stretching ...