Isomer-Specific IR-IR Double. Resonance Spectroscopy of D2-Tagged Protonated Dipeptides Prepared in a Cryogenic Ion Trap

Isomer-specific vibrational predissociation spectra are reported for the gas-phase GlySarH(+) and SarSarH* [Gly = glycine; Sar = sarcosine] ions prepared by electrospray ionization and tagged with wealdy bound D-2 adducts using a cryogenic ion trap. The contributions of individual isomers to the overlapping vibrational band patterns are completely isolated using a pump-probe photochemical hole-burning scheme involving two tunable infrared lasers and two stages of mass selection (hence (IRMS2)-M-2). These patterns are then assigned by comparison with harmonic (MP2/6-311+G(d,p)) spectra for various possible conformers. Both systems occur in two conformations based on cis and trans configurations with respect to the amide bond. In addition to the usual single intramolecular hydrogen bond motif between the protonated amine and the nearby amide oxygen atom, cis-SarSarH(+) adopts a previous unreported conformation in which both amino NH's act as H-bond donors. The correlated red shifts in the NH donor and C=O acceptor components of the NH center dot center dot center dot O=C linkage to the acid group are unambiguously assigned in the double H-bonded conformer.