Cascade Infrared Thermal Photon Emission.

The later stages of cooling of molecules and clusters in the interstellar medium are dominated by emission of vibrational infrared radiation. With the development of cryogenic storage it has become possible to experimentally study these processes. Recent storage ring results demonstrate that intramolecular vibrational redistribution takes place within the cooling process, and an harmonic cascade model has been used to interpret the data. Here we analyze this model and show that the energy distributions and the photon emission rates develop into near-universal functions that can be characterized with only a few parameters, irrespective of the precise vibrational spectra and oscillator strengths of the systems. We show that the photon emission rate and emitted power vary linearly with total excitation energy with a small offset. The time developments of ensemble internal energy distributions are calculated with respect to their first two moments. The excitation energy decreases exponentially with a rate constant which is the average of all k1→0 Einstein coefficients, and the time development of the variance is also calculated.

Peptide Bond Formation in the Protonated Serine Dimer Following Vacuum UV Photon-Induced Excitation.

Possible routes for intra-cluster bond formation (ICBF) in protonated serine dimers have been studied. We found no evidence of ICBF following low energy collision-induced dissociation (in correspondence with previous works), however, we do observe clear evidence for ICBF following photon absorption in the 4.6-14 eV range. Moreover, the comparison of photon-induced dissociation measurements of the protonated serine dimer to those of a protonated serine dipeptide provides evidence that ICBF, in this case, involves peptide bond formation (PBF). The experimental results are supported by ab initio molecular dynamics and exploration of several excited state potential energy surfaces, unraveling a pathway for PBF following photon absorption. The combination of experiments and theory provides insight into the PBF mechanisms in clusters of amino acids, and reveals the importance of electronic excited states reached upon UV/VUV light excitation.