Attosecond transient absorption spooktroscopy: a ghost imaging approach to ultrafast absorption spectroscopy

The recent demonstration of isolated attosecond pulses from an X-ray free-electron laser (XFEL) opens the possibility for probing ultrafast electron dynamics at X-ray wavelengths. An established experimental method for probing ultrafast dynamics is X-ray transient absorption spectroscopy, where the X-ray absorption spectrum is measured by scanning the central photon energy and recording the resultant photoproducts. The spectral bandwidth inherent to attosecond pulses is wide compared to the resonant features typically probed, which generally precludes the application of this technique in the attosecond regime. In this paper we propose and demonstrate a new technique to conduct transient absorption spectroscopy with broad bandwidth attosecond pulses with the aid of ghost imaging, recovering sub-bandwidth resolution in photoproduct-based absorption measurements.

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

Design, Fabrication and Characterization of Mid-Infrared Strip Waveguide for Laser Spectroscopy in Liquid Environments

Yu-Chi Chang

Optical sensors based on the interaction between molecular vibrations and mid infrared radiations attracted high attentions in the last decades. In this study, we present the development of a waveguide evanescent field sensor based on the absorption spectroscopy in liquid environments. The device consists of a single mode strip waveguide integrated with a microfluidic system. With a quantum cascade laser at the wavelength of 5.8 μm, we demonstrate the detection of cocaine dissolved in tetrachloroethylene (PCE). Mid infrared germanium waveguides on silicon have been proposed but not experimentally demonstrated. Here we realize this new type of waveguide with a monocrystalline germanium layer on a silicon substrate (Ge-on-Si) with standard photolithography and reactive ion etching. It is designed to be singlemode in transverse magnetic polarization at 5.8 μm. We used a method based on the Fabry-Perot resonance to measure the propagation loss, and the achieved lowest loss is 2.4 dB/cm. The bending loss was measured to be 0.12 dB per 90∘bend with the radius of 115 μm. A microfluidic chip made from a UV-curable adhesive is integrated to the Ge-on- Si waveguide. This is the first integration of this waveguide with a microfluidic system. Solutions of cocaine in PCE flow in the microfluidic channel and absorb the light in the evanescent field. A reference waveguide and an integrated Y- junction eliminate the noise from coupling fluctuations, and the limit of detection is calculated to be 5 μg/ml. Mid infrared photonics can be further developed based on the platform of Ge-on- Si waveguides. We demonstrate a detection of refractive index changes with a Mach-Zehnder interferometer integrated with a microfluidic system. Subwavelength structures for antireflection of the waveguide facets are also experimentally tested. We foresee an increasing development and applications based on this waveguide in the mid infrared.

EPFL2012

A proposal for fs-electron microscopy experiments on high-energy excitations in solids

Fabrizio Carbone, Luca Piazza

Recent advances in ultrafast technology enable both the study and the control of materials properties thanks to the ability to record high temporal resolution movies of their transformations, or the ability to generate new states of matter by selecting ad hoc an excitation to drive the system out of equilibrium. The holy grail of this type of experiments is to combine a high tuneability of the excitation with a wide observation window. For example, this is achieved in multidimensional optical spectroscopy where the response to several excitation energies is monitored in a broad energy range by a large bandwidth optical pulse. In this article, the possibility to combine the chemical sensitivity of intense tuneable X-rays pulses from a free electron laser, with the wide range of observables available in an ultrafast transmission electron microscope is discussed. The requirements for such experiments are quantified via estimates based on state of the art experiments and simulations, and it is proposed that ultrafast electron imaging, diffraction and spectroscopy experiments can be performed in combination with a chemically selective X-ray excitation of materials. (C) 2014 The Authors. Published by Elsevier Ltd. All rights reserved.

Pergamon-Elsevier Science Ltd2014

Design, Fabrication and Characterization of Mid-Infrared Strip Waveguide for Laser Spectroscopy in Liquid Environments

Yu-Chi Chang

EPFL2012

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

Georgios Papadopoulos

EPFL2012