Spectroscopy of 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) attached to rare gas samples: Clusters vs. bulk matrices. I. Absorption spectroscopy

The interaction between 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) and rare gas or para-hydrogen samples is studied by means of laser-induced fluorescence excitation spectroscopy. The comparison between spectra of PTCDA embedded in a neon matrix and spectra attached to large neon clusters shows that these large organic molecules reside on the surface of the clusters when doped by the pick-up technique. PTCDA molecules can adopt different conformations when attached to argon, neon, and para-hydrogen clusters which implies that the surface of such clusters has a well-defined structure without liquid or fluxional properties. Moreover, a precise analysis of the doping process of these clusters reveals that the mobility of large molecules on the cluster surface is quenched, preventing agglomeration and complex formation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4759443]

Spectroscopy of 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) attached to rare gas samples: Clusters vs. bulk matrices. II. Fluorescence emission spectroscopy

Matthieu Dvorak, Wolfgang Harbich, Stefan Minniberger, Alexandre Rydlo

The interaction between 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) molecules and solid rare gas samples is studied by means of fluorescence emission spectroscopy. Laser-excited PTCDA-doped large argon, neon, and para-hydrogen clusters along with PTCDA embedded in helium nanodroplets are spectroscopically characterized with respect to line broadening and shifting. A fast non-radiative relaxation is observed before a radiative decay in the electronic ground state takes place. In comparison, fluorescence emission studies of PTCDA embedded in bulk neon and argon matrices result in much more complex spectral signatures characterized by a splitting of the different emission lines. These can be assigned to the appearance of site isomers of the surrounding matrix lattice structure. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4759445]

American Institute of Physics2012

A Combination of Cold Ion Spectroscopy and Ion Mobility for the Study of Complex Peptides and Small Proteins

Georgios Papadopoulos

We present in this work experiments that push the limits of cold ion spectroscopy to the study of complex peptides and small proteins in the gas phase. Although the low temperature attainable in a cold ion trap greatly simplifies the electronic spectra of large molecules, conformational heterogeneity can still be a significant source of congestion, complicating spectroscopic analysis. To overcome this hurdle, we propose an in tandem combination of ion mobility spectrometry and photofragment spectroscopy. This permits for conformational separation prior to laser interrogation. Towards this end, we describe a proof-of-principle experiment where we combine high- Field Asymmetric waveform Ion Mobility Spectrometry (FAIMS) with electronic spectroscopy. We demonstrate that using FAIMS to separate gas-phase peptide conformers before injecting them into a cold ion trap allows one to decompose a dense spectrum into contributions from different conformational families. In the inverse sense, cold ion spectroscopy can be used as a conformation-specific detector for ion mobility, allowing one to separate an unresolved mobility peak into contributions from different conformational families. The doubly protonated peptide bradykinin serves as a good test case for the marriage of these two techniques as it exhibits a considerable degree of conformational heterogeneity that results in a highly congested electronic spectrum. Our results demonstrate the feasibility and advantages of directly coupling ion mobility with spectroscopy and provide a diagnostic of conformational isomerization of this peptide after being produced in the gas phase by electrospray. In a second series of studies we show the potential but also the limitations of our spectroscopic approach for investigating small, naturally occurring proteins, by applying it to ubiquitin, a protein of 76 amino acids. We present electronic photofragment spectra of various protonation states of ubiquitin and we compare our results to literature data acquired by ion mobility spectrometry. These experiments show that the information obtained by laser interrogation of molecules of this size is limited and could be enhanced by a combination with ion mobility techniques. Although some of the results obtained may be important in characterizing small proteins in the gas phase, these experiments are at an early stage and the application of photofragment spectroscopy on proteins needs more investigation.

EPFL2012

Supercontinuum generation in silicon nitride (Si_3N_4) waveguides for middle infrared spectroscopy

Eirini Tagkoudi

The middle-infrared (mid-IR) spectral range hosts the most intense roto-vibrational absorption lines of many important molecules. Particularly, mid-IR spectroscopy constitutes a unique tool for identifying and quantifying molecular species through their mid-IR spectral fingerprints. Exploiting efficient ways to access the mid-IR is of supreme importance for spectroscopic applications and environmental monitoring. Supercontinuum (SC) sources have been a common way to access this spectral region, using femtosecond fiber lasers and optical fibers as the broadening medium. However, emphasis has recently shifted towards compact SC sources based on integrated platforms. Among the different materials studied for the integration of SC, stoichiometric silicon nitride,

\mathrm{Si_3N_4}

, is one of the most promising. With a transparency window extending from the visible to mid-IR, CMOS compatibility, and a mature fabrication technology combined with flexibility in design,

\mathrm{Si_3N_4}

waveguides represent an attractive solution for on-chip SC generation. The thesis's main aim is to develop a tunable mid-IR SC source based on

\mathrm{Si_3N_4}

waveguides that can efficiently reach the spectral region between 3 - 4

\mathrm{\mu m}

, enabling mid-IR spectroscopy experiments. Towards this goal, nonlinear SC dynamics based on anomalous and all-normal-dispersion (ANDi) pumping regimes are explored in different waveguide designs. In the first part of the thesis, the development of a tunable mid-IR source is presented. Starting from a tunable turn-key femtosecond 2

\mathrm{\mu m}

fiber laser located in the anomalous dispersion regime of cladded waveguides, mid-IR soliton-induced dispersive waves (DWs) are generated. A synergy of proper waveguide geometry and pump positioning enables favorable dispersion profiles towards the mid-IR while suppressing the generation into the visible. Moreover, by switching to a waveguide with different dimensions, the DW can be tuned between the entire 3 - 4

\mathrm{\mu m}

spectral region, reaching record efficiencies up to 35%. The milliwatt output powers of the mid-IR DWs guarantee their utilization in gas spectroscopy. In the second part, the application of the on-chip generated mid-IR source in direct absorption spectroscopy is demonstrated for the first time. The most efficient DW generated at 3.0

\mathrm{\mu m}

is used to detect acetylene in a proof-of-principle spectroscopic experiment. However, due to DWs' limited bandwidth, parallel gas detection is not possible. By leveraging a waveguide that generates a DW centered at 3.5

\mathrm{\mu m}

and fine-tuning the pump wavelength, a larger bandwidth of the DW source is achieved, enabling simultaneous detection of multiple gas-phase species. Using the broad mid-IR DW from a single

\mathrm{Si_3N_4}

waveguide, detection of acetylene, methane, and ethane is successfully demonstrated, with hundreds of ppm detection limit. Finally, a polarization-sensitive SC source based on an un-cladded

\mathrm{Si_3N_4}

waveguide is studied. The waveguide is engineered to yield ANDi at 2

\mathrm{\mu m}

for the TM mode and anomalous dispersion regime for TE mode excitation. A flat and highly coherent ANDi SC or an octave-spanning soliton fission-driven SC source can be selectively generated by simply switching between the pump's polarization states. As a result, the SC has the potential for versatile applications, from broadband on-chip sensing to pulse compression.

EPFL2021