Femtosecond Spectroscopy with Vacuum Ultraviolet Pulse Pairs

We combine different wavelengths from an intense high-order harmonics source with variable delay at the focus of a split-mirror interferometer to conduct pump-probe experiments on gas-phase molecules. We report measurements of the time resolution (<44 fs) and spatial profiles (4 {\mu}m x 12 {\mu}m) at the focus of the apparatus. We demonstrate the utility of this two-color, high-order-harmonic technique by time resolving molecular hydrogen elimination from C2H4 excited into its absorption band at 161 nm

Measuring laser carrier-envelope-phase effects in the noble gases with an atomic hydrogen calibration standard

We present accurate measurements of carrier-envelope-phase effects on ionization of the noble gases with few-cycle laser pulses. The experimental apparatus is calibrated by using atomic hydrogen data to remove any systematic offsets and thereby obtain accurate CEP data on other generally used noble gases such as Ar, Kr, and Xe. Experimental results for H are well supported by exact time-dependent Schrödinger equation theoretical simulations; however, significant differences are observed in the case of the noble gases.Griffith Sciences, School of Natural SciencesFull Tex

Ultrafast Internal Conversion in Ethylene. II. Mechanisms and Pathways for Quenching and Hydrogen Elimination

Through a combined experimental and theoretical approach, we study the nonadiabatic dynamics of the prototypical ethylene (C$_2$H$_4$) molecule upon $\pi \rightarrow \pi^*$ excitation with 161 nm light. Using a novel experimental apparatus, we combine femtosecond pulses of vacuum ultraviolet (VUV) and extreme ultraviolet (XUV) radiation with variable delay to perform time resolved photo-ion fragment spectroscopy. In this second part of a two part series, the extreme ultraviolet (17 eV$< h \nu < 23$ eV) probe pulses are sufficiently energetic to break the C-C bond in photoionization, or photoionize the dissociation products of the vibrationally hot ground state. The experimental data is directly compared to ab initio molecular dynamics simulations accounting for both the pump and probe steps. Enhancements of the CH$_2^+$ and CH$_3^+$ photoion fragment yields, corresponding to molecules photoionized in ethylene (CH$_2$CH$_2$) and ethylidene (CH$_3$CH) like geometries are observed within 100 fs after $\pi \rightarrow \pi^*$ excitation. Quantitative agreement between theory and experiment on the relative CH$_2^+$ and CH$_3^+$ yields provides experimental confirmation of the theoretical prediction of two distinct transition states and their branching ratio (Tao, et al. J. Phys. Chem. A. 113, 13656 (2009)). Fast, non-statistical, elimination of H$_2$ molecules and H atoms is observed in the time resolved H$_2^+$ and H$^+$ signals

Measuring laser carrier-envelope-phase effects in the noble gases with an atomic hydrogen calibration standard

We present accurate measurements of carrier-envelope-phase effects on ionization of the noble gases with few-cycle laser pulses. The experimental apparatus is calibrated by using atomic hydrogen data to remove any systematic offsets and thereby obtain accurate CEP data on other generally used noble gases such as Ar, Kr, and Xe. Experimental results for H are well supported by exact time-dependent Schrödinger equation theoretical simulations; however, significant differences are observed in the case of the noble gases

Ultrafast structure and dynamics in ionic liquids: 2D-IR spectroscopy probes the molecular origin of viscosity

The viscosity of imidazolium ionic liquids increases dramatically when the strongest hydrogen bonding location is methylated. In this work, ultrafast two-dimensional vibrational spectroscopy of dilute thiocyanate ion ([SCN] -) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]) and 1-butyl-2,3- dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C 1C12im][NTf2]) shows that the structural reorganization occurs on a 26 ± 3 ps time scale and on a 47 ± 15 ps time scale, respectively. The results suggest that the breakup of local ion-cages is the fundamental event that activates molecular diffusion and determines the viscosity of the fluids. © 2014 American Chemical Society

Self-corrected chip-based dual-comb spectrometer

Published 30 Mar 2017We present a dual-comb spectrometer based on two passively mode-locked waveguide lasers integrated in a single Er-doped ZBLAN chip. This original design yields two free-running frequency combs having a high level of mutual stability. We developed in parallel a self-correction algorithm that compensates residual relative fluctuations and yields mode-resolved spectra without the help of any reference laser or control system. Fluctuations are extracted directly from the interferograms using the concept of ambiguity function, which leads to a significant simplification of the instrument that will greatly ease its widespread adoption and commercial deployment. Comparison with a correction algorithm relying on a single-frequency laser indicates discrepancies of only 50 attoseconds on optical timings. The capacities of this instrument are finally demonstrated with the acquisition of a high-resolution molecular spectrum covering 20 nm. This new chip-based multi-laser platform is ideal for the development of high-repetition-rate, compact and fieldable comb spectrometers in the near- and mid-infrared.Nicolas Bourbeau Hébert, Jérôme Genest, Jean-Daniel Deschênes, Hugo Bergeron, George Y. Chen, Champak Khurmi, and David G. Lancaste