l0pt Figure One of the most exciting developments in astronomy is the discovery of thousands of planets around stars other than our Sun. But how do these exo-planets form, and which chemical ingredients are available to build them? Thanks to powerful new telescopes, especially the Atacama Large Millimeter/submillimeter Array (ALMA), astronomers are starting to address these age-old questions scientifically. Stars and planets are born in the cold and tenuous clouds between the stars in the Milky Way. In spite of the extremely low temperatures and densities, a surprisingly rich and interesting chemistry occurs in these interstellar clouds, as evidenced by the detection of more than 180 different molecules. Highly accurate spectroscopic data are key to their identification, and examples of the continued need and close interaction between laboratory work and astronomical observations will be given. ALMA now allows us to zoom in on solar system construction for the first time. Spectral scans of the birth sites of young stars contain tens of thousands of rotational lines. Water and a surprisingly rich variety of organic materials are found, including simple sugars and high abundances of deuterated species. How are these molecules formed? Can these pre-biotic molecules end up on new planets and form the basis for life elsewhere in the universe? Stay tuned for the latest analyses and also a comparison with recent results from the Rosetta mission to comet 67 P/C-G in our own Solar System.

Gas phase infrared photodissociation spectroscopy and matrix isolation infrared absorption spectroscopy have proven to be effective spectroscopic methods to investigate novel molecular and cluster species. Vibrational spectroscopy combined with state-of-the-art quantum chemical calculations provides detailed information on geometric and electronic structures as well as chemical bonding of the observed species. In this presentation, I will highlight our recent studies on the formation and infrared spectroscopic characterization of a number of neutral and charged metal-containing compounds including high oxidation state transition metal and lanthanide oxide species and metal carbonyl clusters featuring unprecedented metal-metal multiple bonds. These findings help to expand chemical understanding of the behavior of elements and their compounds.

Time-resolved coherent spectroscopy has opened many new directions to study ultrafast dynamics in complex quantum systems. While most applications have been achieved in the condensed phase, we are focusing on dilute gas phase samples, in particular, on doped helium droplet beams. Isolation in such droplets at millikelvin temperatures provides unique opportunities to synthesize well-defined complexes, to prepare specific ro-vibronic states, and study their dynamics. To account for the small densities in our samples, we apply a phase modulation technique in order to reach enough sensitivity and a high spectral resolution in electronic wave packet interferometry experiments. The combination with mass-resolved ion detection enabled us e.g. to characterize vibrational structures of excimer molecules. By extending this technique we have observed collective resonances in samples of very low density (10⁸ cm⁻³). With a variant of this method, we are currently elaborating the implementation of nonlinear all-XUV spectroscopy.

Ion traps provide a great environment for carrying out controlled ion-neutral molecular reactions. They not only allow for low-temperature chemistry but also for the formation of weakly-bound clusters suitable for vibrational predissociation spectroscopy. Here we present a novel dual cryogenic ion trap spectrometer which combines both capabilities. The first ion trap allows for temperature controlled (77-300K) ion-neutral reaction and clustering, while the second ion trap further thermalize (10K) the reacted complexes and prepare them for subsequent infrared vibrational predissociation characterization. Our studies show that at 80K, large solvated clusters with more than 50 water molecules can be formed around almost any ions inside the first ion trap. This opens the door for studies of peptide structures as a function of solvation. Preliminary data on the microsolvation of model protonated (Gly)_n peptides will be presented. One complication in these studies is the presence of multiple conformations and resulting spectral congestion which hinders the spectral analysis. We approached this issue in two different ways. First, taking advantage of temperature dependent H-D exchange, we formed D₂O solvated all H peptides and thus separated the spectral signatures of the solvent and solute into two different regions. Second, implementation of a simplified IR-IR double resonance scheme allowed us to efficiently extract conformation-specific spectrum from complex mixture of isobaric molecules. The combination of these two approaches opens the possibility of studying very complex clusters with high structural specificity.

Rovibronic structure of molecules in orbitally degenerate electronic states including Renner-Teller (RT) and Jahn-Teller (JT) active molecules has been extensively studied. Less is known about rotational structure of polyatomic molecules in nearly degenerate states, especially those with low (e.g., C_s) symmetry that are subject to the pseudo-Jahn-Teller (pJT) effect. In the case of free radicals, the unpaired electron further complicates energy levels by inducing spin-orbit (SO) and spin-rotation (SR) splittings. Asymmetric deuteration or methyl substitution of C_3v free radicals such as CH₃O, CaCH₃, and CaOCH₃ lowers the molecular symmetry, lifts the vibronic degeneracy, and reduces the JT effect to the pJT effect. New spectroscopic models are required to reproduce the rovibronic structure and simulate the experimentally obtained spectra of pJT-active free radicals. It has been found that rotational and fine-structure analysis of spectra involving nearly degenerate states may aid in vibronic analysis and interpretation of effective molecular constants. Especially, SO and Coriolis interactions that couple the two states can be determined accurately from fitting the experimental spectra. Coupling between the two electronic states also affects the intensities of rotational and vibronic transitions. The study on free radicals in nearly degenerate states provides a promising avenue of research which may bridge the gap between symmetry-induced degenerate states and the Born-Oppenheimer (BO) limit of unperturbed electronic states.