Cryogenic Ion Vibrational Spectroscopy of Protonated Valine: Messenger Tag Effects

We report the infrared photodissociation spectrum of tagged protonated valine in the range 1000 – 1900 cm-1, prepared in a cryogenic ion trap. Comparison of experimental results with calculated infrared spectra based on density functional theory shows that the hydroxyl group of the carboxylic acid functionality and the protonated amine group adopt a trans configuration. Nitrogen and methane molecules were used as messenger tags, with optimal tagging temperatures of 30 K for N2 and 60 K for CH4. While the calculated infrared spectra of the tagged ion suggest only a weak influence of the messenger tag on the frequency positions of ValH+, the measured intensities for N2-tagged ValH+ are strongly suppressed for all but the highest frequency features at 1773 cm-1. We trace this behavior to the binding energy of the N2 tag, which is significantly higher than that of CH4, based on CCSD(T) calculations and rate estimates for photoinduced unimolecular dissociation from statistical theory.