Ultrafast processes in matter, such as the electron emission after light absorption, can now be studied using ultrashort light pulses of attosecond duration (10−18 seconds) in the extreme ultraviolet ...spectral range. The lack of spectral resolution due to the use of short light pulses has raised issues in the interpretation of the experimental results and the comparison with theoretical calculations. We determine photoionization time delays in neon atoms over a 40–electron volt energy range with an interferometric technique combining high temporal and spectral resolution. We spectrally disentangle direct ionization from ionization with shake-up, in which a second electron is left in an excited state, and obtain excellent agreement with theoretical calculations, thereby solving a puzzle raised by 7-year-old measurements.
Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms ...often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. High-level-coupled cluster calculations confirm the method's impressive electronic structure sensitivity for excited-state investigations.Many photo-induced processes such as photosynthesis occur in organic molecules, but their femtosecond excited-state dynamics are difficult to track. Here, the authors exploit the element and site selectivity of soft X-ray absorption to sensitively follow the ultrafast ππ*/nπ* electronic relaxation of hetero-organic molecules.
Free-electron lasers providing ultra-short high-brightness pulses of X-ray radiation have great potential for a wide impact on science, and are a critical element for unravelling the structural ...dynamics of matter. To fully harness this potential, we must accurately know the X-ray properties: intensity, spectrum and temporal profile. Owing to the inherent fluctuations in free-electron lasers, this mandates a full characterization of the properties for each and every pulse. While diagnostics of these properties exist, they are often invasive and many cannot operate at a high-repetition rate. Here, we present a technique for circumventing this limitation. Employing a machine learning strategy, we can accurately predict X-ray properties for every shot using only parameters that are easily recorded at high-repetition rate, by training a model on a small set of fully diagnosed pulses. This opens the door to fully realizing the promise of next-generation high-repetition rate X-ray lasers.
The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an ...electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220-250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.
The first steps in photochemical processes, such as photosynthesis or animal vision, involve changes in electronic and geometric structure on extremely short time scales. Time-resolved photoelectron ...spectroscopy is a natural way to measure such changes, but has been hindered hitherto by limitations of available pulsed light sources in the vacuum-ultraviolet and soft X-ray spectral region, which have insufficient resolution in time and energy simultaneously. The unique combination of intensity, energy resolution, and femtosecond pulse duration of the FERMI-seeded free-electron laser can now provide exceptionally detailed information on photoexcitation-deexcitation and fragmentation in pump-probe experiments on the 50-femtosecond time scale. For the prototypical system acetylacetone we report here electron spectra measured as a function of time delay with enough spectral and time resolution to follow several photoexcited species through well-characterized individual steps, interpreted using state-of-the-art static and dynamics calculations. These results open the way for investigations of photochemical processes in unprecedented detail.
Understanding molecular femtosecond dynamics under intense X-ray exposure is critical to progress in biomolecular imaging and matter under extreme conditions. Imaging viruses and proteins at an ...atomic spatial scale and on the time scale of atomic motion requires rigorous, quantitative understanding of dynamical effects of intense X-ray exposure. Here we present an experimental and theoretical study of C60 molecules interacting with intense X-ray pulses from a free-electron laser, revealing the influence of processes not previously reported. Our work illustrates the successful use of classical mechanics to describe all moving particles in C60, an approach that scales well to larger systems, for example, biomolecules. Comparisons of the model with experimental data on C60 ion fragmentation show excellent agreement under a variety of laser conditions. The results indicate that this modelling is applicable for X-ray interactions with any extended system, even at higher X-ray dose rates expected with future light sources.
We have performed x-ray two-photon photoelectron spectroscopy using the Linac Coherent Light Source x-ray free-electron laser in order to study double core-hole (DCH) states of CO2, N2O, and N2. The ...experiment verifies the theory behind the chemical sensitivity of two-site DCH states by comparing a set of small molecules with respect to the energy shift of the two-site DCH state and by extracting the relevant parameters from this shift.
Time-frequency representation of autoionization dynamics in helium Busto, D; Barreau, L; Isinger, M ...
Journal of physics. B, Atomic molecular and optical physics/Journal of physics. B, Atomic, molecular and optical physics,
02/2018, Volume:
51, Issue:
4
Journal Article
Peer reviewed
Open access
Autoionization, which results from the interference between direct photoionization and photoexcitation to a discrete state decaying to the continuum by configuration interaction, is a well known ...example of the important role of electron correlation in light-matter interaction. Information on this process can be obtained by studying the spectral, or equivalently, temporal complex amplitude of the ionized electron wave packet. Using an energy-resolved interferometric technique, we measure the spectral amplitude and phase of autoionized wave packets emitted via the sp2+ and sp3+ resonances in helium. These measurements allow us to reconstruct the corresponding temporal profiles by Fourier transform. In addition, applying various time-frequency representations, we observe the build-up of the wave packets in the continuum, monitor the instantaneous frequencies emitted at any time and disentangle the dynamics of the direct and resonant ionization channels.
We present a combined experimental and theoretical study of single-photon ionization of 9-methyladenine (9MA) in the gas phase. In addition to tautomerism, several rotamers due to the rotation of the ...methyl group may exist. Computations show, however, that solely one rotamer contributes because of low population in the molecular beam and/or unfavorable Franck-Condon factors upon ionization. Experimentally, we used VUV radiation available at the DESIRS beamline of the synchrotron radiation facility SOLEIL to record the threshold photoelectron spectrum of this molecule between 8 and 11 eV. This spectrum consists of a well-resolved band assigned mainly to vibronic levels of the D
cationic state, plus a contribution from the D
state, and two large bands corresponding to the D
, D
and D
electronically excited states. The adiabatic ionization energy of 9MA is measured at 8.097 ± 0.005 eV in close agreement with the computed value using the explicitly correlated coupled cluster approach including core valence, scalar relativistic and zero-point vibrational energy corrections. This work sheds light on the complex pattern of the lowest doublet electronic states of 9MA
. The comparison to canonical adenine reveals that methylation induces further electronic structure complication that may be important to understand the effects of ionizing radiation and the charge distribution in these biological entities at different time scales.
Abstract
Using multi-electron–ion coincidence measurements combined with high level calculations, we show that double ionisation of SO
2
at 40.81 eV can be state selective. It leads to high energy ...products, in good yield, via a newly identified mechanism, which is likely to apply widely to multiple ionisation by almost all impact processes.
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