arXiv subjects

L. Nahon

Publications and source records attributed to L. Nahon.

10 recordsLinked to original sources

arXiv2022

Time-resolved chiral X-Ray photoelectron spectroscopy with transiently enhanced atomic site-selectivity: a Free Electron Laser investigation of electronically excited fenchone enantiomers

Chiral molecules are widespread in nature, playing a fundamental role in bio-chemical processes and in the origin of life itself. The observation of dynamics in chiral molecules is crucial for the understanding and control of the chiral activity of photo-excited states. One of the most promising techniques for the study of photo-excited chiral systems is time-resolved photoelectron circular dichroism (TR-PECD), which offers an intense and sensitive probe for vibronic and geometric molecular structure as well as electronic structures, and their evolution on a femtosecond timescale. However, the non-local character of the PECD effect, which is imprinted during the electron scattering off the molecule, makes the interpretation of TR-PECD experiments challenging. In this respect, core-photoionization is known to allow site- and chemical-sensitivity to photelectron spectroscopy. Here we demonstrate that TR-PECD utilising core-level photoemission enables probing the chiral electronic structure and its relaxation dynamics with atomic site sensitivity. Following UV pumped excitation to a 3s Rydberg state, fenchone enantiomers (C 10 H 16 O) were probed on a femtosecond scale using circularly polarized soft X-ray light pulses provided by the free-electron laser FERMI. C 1s binding energy shifts caused by the redistribution of valence electron density in this 3s-valence-Rydberg excitation allowed us to measure transient PECD chiral responses with an enhanced C-atom site-selectivity compared to that achievable in the ground state molecule. These results represent the first chemical-specific and site-specific, enantio-sensitive observations on the electronic structure of a photo-excited chiral molecule and pave the way towards chiral femtochemistry probed by core-level photoemission.

physics.chem-ph↗

arXiv2017

High-resolution one-photon absorption spectroscopy of the $D\,{}^2Σ^- \leftarrow X\,{}^2Π$ system of radical OH and OD

Vacuum-ultraviolet (VUV) photoabsorption spectra were recorded of the $A\,{}^2Σ^+(v'=0)\leftarrow{}X\,{}^2Π(v''=0)$, $D\,{}^2Σ^-(v'=0)\leftarrow{}X\,{}^2Π(v''=0)$ and $D\,{}^2Σ^-(v'=1)\leftarrow{}X\,{}^2Π(v''=0)$ bands of the OH and OD radicals generated in a plasma-discharge source using synchrotron radiation as a background continuum coupled with the VUV Fourier-transform spectrometer on the DESIRS beamline of synchrotron SOLEIL. High-resolution spectra permitted the quantification of transition frequencies, relative $f$-values, and natural line broadening. The $f$-values were absolutely calibrated with respect to a previous measurement of $A\,{}^2Σ^+(v'=0)\leftarrow{}X\,{}^2Π(v''=0)$ ([wang1979]). Lifetime broadening of the excited $D\,{}^2Σ^-(v=0)$ and $D\,{}^2Σ^-(v=1)$ levels is measured for the first time and compared with previous experimental limits, and implies a lifetime 5 times shorter than a theoretical prediction ([van_der_loo2005]). A local perturbation of the $D\,{}^2Σ^-(v=0)$ level in OH was found.

physics.atom-ph↗

arXiv2017

Size effect in the ionization energy of PAH clusters

We report the first experimental measurement of the near-threshold photo-ionization spectra of polycyclic aromatic hydrocarbon clusters made of pyrene C16H10 and coronene C24H12, obtained using imaging photoelectron photoion coincidence spectrometry with a VUV synchrotron beamline. The experimental results of the ionization energy are confronted to calculated ones obtained from simulations using dedicated electronic structure treatment for large ionized molecular clusters. Experiment and theory consistently find a decrease of the ionization energy with cluster size. The inclusion of temperature effects in the simulations leads to a lowering of this energy and to a quantitative agreement with the experiment. In the case of pyrene, both theory and experiment show a discontinuity in the IE trend for the hexamer.

physics.chem-ph↗

arXiv2016

Photoexcitation Circular Dichroism in Chiral Molecules

Chirality is ubiquitous in nature and fundamental in science, from particle physics to metamaterials.The most established technique of chiral discrimination - photoabsorption circular dichroism - relies on the magnetic properties of a chiral medium and yields an extremely weak chiral response. We propose and demonstrate a new, orders of magnitude more sensitive type of circular dichroism in neutral molecules: photoexitation circular dichroism. It does not rely on weak magnetic effects, but takes advantage of the coherent helical motion of bound electrons excited by ultrashort circularly polarized light. It results in an ultrafast chiral response and the efficient excitation of a macroscopic chiral density in an initially isotropic ensemble of randomly oriented chiral molecules. We probe this excitation without the aid of further chiral interactions using linearly polarized laser pulses. Our time-resolved study of vibronic chiral dynamics opens a way to the efficient initiation, control and monitoring of chiral chemical change in neutral molecules at the level of electrons.

physics.atm-clus↗

arXiv2014

Precision spectroscopy of the $X\,^{1}Σ_{g}^{+}, v=0\rightarrow 1$ ($J=0-2$) rovibrational splittings in H$_{2}$, HD and D$_{2}$

Accurate experimental values for the vibrational ground tone or fundamental vibrational energy splitting of H$_2$, HD, and D$_2$ are presented. Absolute accuracies of $2\times10^{-4}$ cm$^{-1}$ are obtained from Doppler-free laser spectroscopy applied in a collisionless environment. The vibrational splitting frequencies are derived from the combination difference between separate electronic excitations from the $X^{1}Σ_{g}^{+}, v=0, J$ and $v=1, J$ vibrational states to a common $EF^{1}Σ^{+}_{g}, v=0, J$ state. The present work on rotational quantum states $J=1,2$ extends the results reported by Dickenson et al. on $J=0$ [Phys. Rev. Lett. 110 (2013) 193601]. The experimental procedures leading to this high accuracy are discussed in detail. A comparison is made with full \emph{ab initio} calculations encompassing Born-Oppenheimer energies, adiabatic and non-adiabatic corrections, as well as relativistic corrections and QED-contributions. The present agreement between the experimental results and the calculations provides a stringent test on the application of quantum electrodynamics in molecules. Furthermore, the combined experimental-theoretical uncertainty can be interpreted to provide bounds to new interactions beyond the Standard Model of Physics or fifth forces between hadrons.

physics.atom-ph↗

arXiv2013

Novel techniques in VUV high-resolution spectroscopy

Novel VUV sources and techniques for VUV spectroscopy are reviewed. Laser-based VUV sources have been developed via non-linear upconversion of laser pulses in the nanosecond (ns), the picosecond (ps), and femtosecond (fs) domain, and are applied in high-resolution gas phase spectroscopic studies. While the ns and ps pulsed laser sources, at Fourier-transform limited bandwidths, are used in wavelength scanning spectroscopy, the fs laser source is used in a two-pulse time delayed mode. In addition a Fourier-transform spectrometer for high resolution gas-phase spectroscopic studies in the VUV is described, exhibiting the multiplex advantage to measure many resonances simultaneously.

physics.optics↗

arXiv2013

Synchrotron VUV radiation studies of the D^1Π_u State of H_2

The 3pπD^1Π_u state of the H_2 molecule was reinvestigated with different techniques at two synchrotron installations. The Fourier-Transform spectrometer in the vacuum ultraviolet wavelength range of the DESIRS beamline at the SOLEIL synchrotron was used for recording absorption spectra of the D^1Π_u state at high resolution and high absolute accuracy, limited only by the Doppler contribution at 100 K. From these measurements line positions were extracted, in particular for the narrow resonances involving ^1Π_u^- states, with an accuracy estimated at 0.06 cm^{-1} . The new data also closely match MQDT-calculations performed for the Π^- components observed via the narrow Q-lines. The Λ-doubling in the D^1Π_u state was determined up to v=17. The 10 m normal incidence scanning monochromator at the beamline U125/2 of the BESSY II synchrotron, combined with a home built target chamber and equipped with a variety of detectors was used to unravel information on ionization, dissociation and intramolecular fluorescence decay for the D^1Π_u vibrational series. The combined results yield accurate information of the characteristic Beutler-Fano profiles associated with the strongly predissociated Π_u^+ parity components of the D^1Π_u-levels. Values for the parameters describing the predissociation width as well as the Fano-q line shape parameters for the J=1 and J=2 rotational states were determined for the sequence of vibrational quantum numbers up to v=17.

physics.atm-clus↗

arXiv2013

VUV Spectroscopic Study of the D^1ΠState of Molecular Deuterium

The D^1Π_u - X^1Σ_g^+ absorption system of molecular deuterium has been re-investigated using the VUV Fourier -Transform (FT) spectrometer at the DESIRS beamline of the synchrotron SOLEIL and photon-induced fluorescence spectrometry (PIFS) using the 10 m normal incidence monochromator at the synchrotron BESSY II. Using the FT spectrometer absorption spectra in the range 72 - 82 nm were recorded in quasi static gas at 100 K and in a free flowing jet at a spectroscopic resolution of 0.50 and 0.20 cm^{-1} respectively . The narrow Q-branch transitions, probing states of Π^- symmetry, were observed up to vibrational level v = 22. The states of Π^+ symmetry, known to be broadened due to predissociation and giving rise to asymmetric Beutler-Fano resonances, were studied up to v = 18. The 10 m normal incidence beamline setup at BESSY II was used to simultaneously record absorption, dissociation, ionization and fluorescence decay channels from which information on the line intensities, predissociated widths, and Fano q-parameters were extracted. R-branch transitions were observed up to v = 23 for J = 1-3 as well as several transitions for J = 4 and 5 up to v = 22 and 18 respectively. The Q-branch transitions are found to weakly predissociate and were observed from v = 8 to the final vibrational level of the state v = 23. The spectroscopic study is supported by two theoretical frameworks. Results on the Π^- symmetry states are compared to ab initio multi-channel-quantum defect theory (MQDT) calculations, demonstrating that these calculations are accurate to within 0.5 cm^-1.

physics.atm-clus↗

arXiv2012

The CO A-X System for Constraining Cosmological Drift of the Proton-Electron Mass Ratio

The $\textrm{A}^1Π-\textrm{X}^1Σ^+$ band system of carbon monoxide, which has been detected in six highly redshifted galaxies ($z=1.6-2.7$), is identified as a novel probe method to search for possible variations of the proton-electron mass ratio ($μ$) on cosmological time scales. Laboratory wavelengths of the spectral lines of the A-X ($v$,0) bands for $v=0-9$ have been determined at an accuracy of $Δλ/λ=1.5 \times 10^{-7}$ through VUV Fourier-transform absorption spectroscopy, providing a comprehensive and accurate zero-redshift data set. For the (0,0) and (1,0) bands, two-photon Doppler-free laser spectroscopy has been applied at the $3 \times 10^{-8}$ accuracy level, verifying the absorption data. Sensitivity coefficients $K_μ$ for a varying $μ$ have been calculated for the CO A-X bands, so that an operational method results to search for $μ$-variation.

physics.atom-ph↗

arXiv2012

High-resolution Fourier-transform XUV photoabsorption spectroscopy of 14N15N

The first comprehensive high-resolution photoabsorption spectrum of 14N15N has been recorded using the Fourier-transform spectrometer attached to the Desirs beamline at the Soleil synchrotron. Observations are made in the extreme ultraviolet (XUV) and span 100,000-109,000 cm-1 (100-91.7 nm). The observed absorption lines have been assigned to 25 bands and reduced to a set of transition energies, f values, and linewidths. This analysis has verified the predictions of a theoretical model of N2 that simulates its photoabsorption and photodissociation cross section by solution of an isotopomer independent formulation of the coupled-channel Schroedinger equation. The mass dependence of predissociation linewidths and oscillator strengths is clearly evident and many local perturbations of transition energies, strengths, and widths within individual rotational series have been observed.

physics.atm-clus↗