Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity

Photoelectron circular dichroism (PECD) manifests itself as an intense forward/backward asymmetry in the angular distribution of photoelectrons produced from randomly-oriented enantiomers by photoionization with circularly-polarized light (CPL). As a sensitive probe of both photoionization dynamics and of the chiral molecular potential, PECD attracts much interest especially with the recent performance of related experiments with visible and VUV laser sources. Here we report, by use of quasi-perfect CPL VUV synchrotron radiation and using a double imaging photoelectron/photoion coincidence (i2PEPICO) spectrometer, new and very accurate values of the corresponding asymmetries on showcase chiral isomers: camphor and fenchone. These data have additionally been normalized to the absolute enantiopurity of the sample as measured by a chromatographic technique. They can therefore be used as benchmarking data for new PECD experiments, as well as for theoretical models. In particular we found, especially for the outermost orbital of both molecules, a good agreement with CMS-X PECD modeling over the whole VUV range. We also report a spectacular sensitivity of PECD to isomerism for slow electrons, showing large and opposite asymmetries when comparing R-camphor to R-fenchone (respectively -10% and +16 % around 10 eV). In the course of this study, we could also assess the analytical potential of PECD. Indeed, the accuracy of the data we provide are such that limited departure from perfect enantiopurity in the sample we purchased could be detected and estimated in excellent agreement with the analysis performed in parallel via a chromatographic technique, establishing a new standard of accuracy, in the ±1 % range, for enantiomeric excess measurement via PECD. The i2PEPICO technique allows correlating PECD measurements to specific parent ion masses, which would allow its application to analysis of complex mixtures

Transient absorption spectroscopy using high harmonic generation: a review of ultrafast X-ray dynamics in molecules and solids.

Attosecond science opened the door to observing nuclear and electronic dynamics in real time and has begun to expand beyond its traditional grounds. Among several spectroscopic techniques, X-ray transient absorption spectroscopy has become key in understanding matter on ultrafast time scales. In this review, we illustrate the capabilities of this unique tool through a number of iconic experiments. We outline how coherent broadband X-ray radiation, emitted in high-harmonic generation, can be used to follow dynamics in increasingly complex systems. Experiments performed in both molecules and solids are discussed at length, on time scales ranging from attoseconds to picoseconds, and in perturbative or strong-field excitation regimes. This article is part of the theme issue 'Measurement of ultrafast electronic and structural dynamics with X-rays'

Transfer of orbital angular momentum in high harmonic generation using two driving beams

International audienceLight beams may carry both a spin and an orbital angular momentum (OAM). While the former is associated to their polarization state, the latter stems from the geometrical properties of their wavefront. In their prototypical form, beams with OAM have "donuts-like" intensity profile and helicoidal wavefront, carrying integral multiples of h as angular momenta. Since their "rediscovery" in the late 90's, beams with OAM of visible wavelengths have found innumerable applications in quantum optics, microscopy or information transfer. A major recent development was the generation of such beams with much smaller wavelengths - in the extreme ultraviolet (XUV) - using synchrotron sources, free electron lasers as well as high harmonic sources (HHG). In this latter case, it creates ultrashort XUV sources of beams with OAM, suited for time-resolved applications at femtosecond and attosecond time scales. Remarkably, we showed that even though HHG is a non-perturbative process, the OAM transfer from the driving beam to the harmonics was purely parametric; i.e., the q-th harmonic - which can be thought as the upconversion of q infrared photons - carries q times the OAM of the driver [3, 4]. However, this rule limits severely the flexibility in choosing the OAM of the XUV emission

De l’ultra-rapide à l’ultra-intense : de nouveaux champs d’études

International audienceLe développement spectaculaire des lasers de puissance ces trente dernières années a ouvert de nouveaux champs d’études : la science attoseconde d’une part, l’optique relativiste d’autre part. Nous illustrons les nouvelles perspectives ouvertes dans divers domaines de la physique, la chimie, la médecine ou la science des matériaux à partir d’études effectuées sur les plateformes ATTOLab et UHI100 du Laboratoire Interactions, Dynamiques et Lasers (LIDYL) du CEA Paris-Saclay

Beam optimization in a 25 TW femtosecond laser system for high harmonic generation

It has been demonstrated in the past that high fluxes of extreme ultraviolet (XUV) light could be obtained by driving high harmonic generation (HHG) with high energy lasers. However, the peak intensity at the focal point of a femtosecond laser with more than 100 mJ can be too high for phase-matched HHG in gases. We propose a method to optimize the spatial profile at off-focus locations of the high energy driving laser to avoid fully ionizing the target atoms. The beam profile before or after the focal point depends on the wavefront quality of the laser beam and the near field intensity distribution. The beam spot diameter reaches three times that at the focus by adding customized wavefront terms. An XUV pulse energy of 5.6 μJ was obtained from HHG when a larger off-focus spot of a 500 mJ Ti: sapphire laser beam was applied in an argon gas cell

UV-induced dissociation of CH2_2BrI probed by intense femtosecond XUV pulses

The ultraviolet (UV)-induced dissociation and photofragmentation of gas-phase CH$_2$BrI molecules induced by intense femtosecond extreme ultraviolet (XUV) pulses at three different photon energies are studied by multi-mass ion imaging. Using a UV-pump–XUV-probe scheme, charge transfer between highly charged iodine ions and neutral CH$_2$Br radicals produced by C–I bond cleavage is investigated. In earlier charge-transfer studies, the center of mass of the molecules was located along the axis of the bond cleaved by the pump pulse. In the present case of CH$_2$BrI, this is not the case, thus inducing a rotation of the fragment. We discuss the influence of the rotation on the charge transfer process using a classical over-the-barrier model. Our modeling suggests that, despite the fact that the dissociation is slower due to the rotational excitation, the critical interatomic distance for charge transfer is reached faster. Furthermore, we suggest that charge transfer during molecular fragmentation may be modulated in a complex way

Coulomb-explosion imaging of concurrent CH2BrI{\mathbf{CH}}_{2}\mathbf{BrI} photodissociation dynamics

Citation: Burt, M., Boll, R., Lee, J. W. L., Amini, K., Köckert, H., Vallance, C., … Rolles, D. (2017). Coulomb-explosion imaging of concurrent ${\mathbf{CH}}_{2}\mathbf{BrI}$ photodissociation dynamics. Physical Review A, 96(4), 043415. https://doi.org/10.1103/PhysRevA.96.043415The dynamics following laser-induced molecular photodissociation of gas-phase CH2BrI at 271.6 nm were investigated by time-resolved Coulomb-explosion imaging using intense near-IR femtosecond laser pulses. The observed delay-dependent photofragment momenta reveal that CH2BrI undergoes C-I cleavage, depositing 65.6% of the available energy into internal product states, and that absorption of a second UV photon breaks the C-Br bond of CH2Br. Simulations confirm that this mechanism is consistent with previous data recorded at 248 nm, demonstrating the sensitivity of Coulomb-explosion imaging as a real-time probe of chemical dynamics