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Local probes of the electronic ground state are essential for understanding hydrogen bonding in aqueous environments. When tuned to the dissociative core-excited state at the O1 s pre-edge of water, resonant inelastic X-ray scattering back to the electronic ground state exhibits a long vibrational progression due to ultrafast nuclear dynamics. We show how the coherent evolution of the OH bonds around the core-excited oxygen provides access to high vibrational levels in liquid water. The OH bonds stretch into the long-range part of the potential energy curve, which makes the X-ray probe more sensitive than infra-red spectroscopy to the local environment. We exploit this property to effectively probe hydrogen bond strength via the distribution of intramolecular OH potentials derived from measurements. In contrast, the dynamical splitting in the spectral feature of the lowest valence-excited state arises from the short-range part of the OH potential curve and is rather insensitive to hydrogen bonding. Understanding how nuclear motions affect vibrational motions in molecular liquids remains challenging in modern condensed matter physics. Here the authors study the vibrational quantum effects in liquid water and show the sensitivity on the coherent evolution of OH bonds in core-excited states.

Resonant inelastic x-ray scattering (RIXS) is a well-established tool for studying electronic, nuclear, and collective dynamics of excited atoms, molecules, and solids. An extension of this powerful method to a time-resolved probe technique at x-ray free electron lasers (XFELs) to ultimately unravel ultrafast chemical and structural changes on a femtosecond time scale is often challenging, due to the small signal rate in conventional implementations at XFELs that rely on the usage of a monochromator setup to select a small frequency band of the broadband, spectrally incoherent XFEL radiation. Here, we suggest an alternative approach, based on stochastic spectroscopy, which uses the full bandwidth of the incoming XFEL pulses. Our proposed method is relying on stimulated resonant inelastic x-ray scattering, where in addition to a pump pulse that resonantly excites the system a probe pulse on a specific electronic inelastic transition is provided, which serves as a seed in the stimulated scattering process. The limited spectral coherence of the XFEL radiation defines the energy resolution in this process and stimulated RIXS spectra of high resolution can be obtained by covariance analysis of the transmitted spectra. We present a detailed feasibility study and predict signal strengths for realistic XFEL parameters for the CO molecule resonantly pumped at the O 1 s → π * transition. Our theoretical model describes the evolution of the spectral and temporal characteristics of the transmitted x-ray radiation, by solving the equation of motion for the electronic and vibrational degrees of freedom of the system self consistently with the propagation by Maxwell equations.

Quenching of vibrational excitations in resonant inelastic X-ray scattering (RIXS) spectra of liquid acetic acid is observed. At the oxygen core resonance associated with localized excitations at the O–H bond, the spectra lack the typical progression of vibrational excitations observed in RIXS spectra of comparable systems. We interpret this phenomenon as due to strong rehybridization of the unoccupied molecular orbitals as a result of hydrogen bonding, which however cannot be observed in x-ray absorption but only by means of RIXS. This allows us to address the molecular structure of the liquid, and to determine a lower limit for the average molecular chain length.

The dynamics of fragmentation and vibration of molecular systems with a large number of coupled degrees of freedom are key aspects for understanding chemical reactivity and properties. Here we present a resonant inelastic X-ray scattering (RIXS) study to show how it is possible to break down such a complex multidimensional problem into elementary components. Local multimode nuclear wave packets created by X-ray excitation to different core-excited potential energy surfaces (PESs) will act as spatial gates to selectively probe the particular ground-state vibrational modes and, hence, the PES along these modes. We demonstrate this principle by combining ultra-high resolution RIXS measurements for gas-phase water with state-of-the-art simulations. Investigating dynamics of polyatomic molecules is difficult as their potential energy surfaces are multidimensional due to coupled degrees of freedom. Here the authors demonstrate a spatial selective gating technique to probe the different vibrational modes of water upon core-level excitation with X-rays.

In theoretical simulations of a UV + x-ray pump-probe (UVX-PP) setup, we show that frequency detuning of the pump UV pulse acts as a camera shutter by regulating the duration of the UVX-PP process. This two-photon absorption with long overlapping UV and x-ray pulses, allowing for high spectral resolution, thereby provides information about ultrafast dynamics of the nuclear wave packet without the requirement of ultrashort pulses and controlled delay times. In a case study of carbon monoxide, the calculated UVX-PP spectra of the O1 s −1 2 π 1 and C1 s −1 2 π 1 core-excited states show different vibrational profiles. The interference of intermediate vibrational states reveals details of nuclear dynamics in the UVX-PP process related to a variable duration time controlled by the UV detuning. Both O1 s −1 2 π 1 and C1 s −1 2 π 1 pump-probe channels display a splitting of the spectral profile, which however is associated with different physical mechanisms. At the O1 s −1 2 π 1 resonance, the observed dispersive and non-dispersive spectral bands intersect and result in destructive interference.

Ultraviolet (UV) photodissociation provides valuable insights into fragmentation patterns and photochemical reactions. However, the limited overlap between vibrational bound states and continuum states hinders efficient quantum excitation. We address this challenge by embedding the ground bound potential into the dissociative continuum using a frequency-selected UV pulse. This pulse creates vibrational resonances by coupling the dissociative continuum with unpopulated vibrationally excited levels of the ground state, without initiating photoexcitation itself. Our findings demonstrate that the photodissociation spectra can be significantly manipulated by tuning the embedding pulse frequency to tailor the asymmetric profiles of the vibrational resonances. This is illustrated in our simulations of kinetic energy release spectra for both diatomic and polyatomic molecules. These proof-of-principle examples offer opportunities for manipulating the yield of photofragmentation and the pathways of photochemical reactions in various molecular systems. The quantum excitation of photodissociation is restricted by the overlap between vibrational bound and continuum states. The authors manipulate the dynamics by generating new vibrational Fano resonances and controlling the asymmetric profiles of these resonances using an embedded ultraviolet pulse.

Time-resolved X-ray photoelectron spectroscopy (TXPS) is a well-established technique to probe coherent nuclear wavepacket dynamics using both table-top and free-electron-based ultrafast X-ray lasers. Energy resolution, however, becomes compromised for a very short pulse duration in the sub-femtosecond range. By resonantly tuning the X-ray pulse to core-excited states undergoing Auger decay, this drawback of TXPS can be mitigated. While resonant Auger-electron spectroscopy (RAS) can recover the vibrational structures not hidden by broadband excitation, the full reconstruction of the wavepacket is a standing challenge. Here, we theoretically demonstrate how the complete information of a nuclear wavepacket, i.e., the populations and relative phases of the vibrational states constituting the wavepacket, can be retrieved from time-resolved RAS (TRAS) measurements. Thus, TRAS offers key insights into coupled nuclear and electronic dynamics in complex systems on ultrashort timescales, providing an alternative to leverage femtosecond and attosecond X-ray probe pulses. Resorting to resonant Auger spectroscopy mitigates the energy resolution limit of time-resolved X-ray photoelectron spectroscopy, but reconstructing the full nuclear wavepacket evolution from it is an open challenge. The authors retrieve the full information of a nuclear wavepacket from time-resolved resonant Auger spectroscopy measurements.

Carrier-envelope-phase (CEP) of sub-cycle ultraviolet (UV) pulse strongly influences the dynamics of quantum systems, but its characterization is not accessible experimentally. Here we investigate photodissociation of a diatomic molecule from its ground-rovibrational state in a linearly polarized weak sub-cycle UV pulse with a controlled CEP. The angular distribution of photofragments shows an asymmetric profile deviating from the well-known cos 2 - or sin 2 -like ones, which can be identified as a way to imprint CEP. We unveil that such an effect stems from the temporal neighboring rotational excitation by molecular permanent dipole interaction through the joint contributions between counter-rotating and rotating terms. This in turn, opens different pathways in photodissociation dynamics. Given that the temporal excitation between various states with close energies can be manipulated by CEP of sub-cycle UV pulses, our results pave ways for understanding and manipulating electron, nuclear and their joint dynamics with variation of CEP of attosecond pulses. The carrier-envelope-phase of sub-cycle UV pulses strongly influences the dynamics of quantum systems, but its characterization is not accessible experimentally. Here, an asymmetry in the of angular photofragment distributions of diatomic molecules is identified as a way to imprint carrier-envelope-phase on a measurable quantity.

We consider resonances induced by symmetry protected bound states in the continuum in dielectric gratings with in-plane mirror symmetry. It is shown that the shape of the resonance in transmittance is controlled by two parameters in a generic formula which can be derived in the framework of the coupled mode theory. It is numerically demonstrated that the formula encompasses various line-shapes including asymmetric Fano, Lorentzian, and anti-Lorentzian resonances. It is confirmed that the transmittance zeros are always present even in the absence up-down symmetry. At the same time reflectance zeros are not generally present in the single mode approximation. It is found that the line-shapes of Fano resonances can be predicted to a good accuracy by the random forest machine learning method which outperforms the standard least square methods approximation in error by an order of magnitude in error with the training dataset size .