Attosecond-pump attosecond-probe x-ray spectroscopy of liquid water

Developing a molecular-level understanding of the properties of water is central to numerous scientific and technological applications. However, accurately modeling water through computer simulations has been a significant challenge due to the complex nature of the hydrogen-bonding network that water molecules form under different thermodynamic conditions. This complexity has led to over five decades of research and many modeling attempts. The introduction of the MB-pol data-driven many-body potential energy function marked a significant advancement toward a universal molecular model capable of predicting the structural, thermodynamic, dynamical, and spectroscopic properties of water across all phases. By integrating physics-based and data-driven (i.e., machine-learned) components, which correctly capture the delicate balance among different many-body interactions, MB-pol achieves chemical and spectroscopic accuracy, enabling realistic molecular simulations of water, from gas-phase clusters to liquid water and ice. In this review, we present a comprehensive overview of the data-driven many-body formalism adopted by MB-pol, highlight the main results and predictions made from computer simulations with MB-pol to date, and discuss the prospects for future extensions to data-driven many-body potentials of generic and reactive molecular systems.

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Attosecond formation of charge-transfer-to-solvent states of aqueous ions probed using the core-hole-clock technique

Muchová,

Gopakumar,

Unger

et al. 2024

Nat Commun

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Charge transfer between molecules lies at the heart of many chemical processes. Here, we focus on the ultrafast electron dynamics associated with the formation of charge-transfer-to-solvent (CTTS) states following X-ray absorption in aqueous solutions of Na+, Mg2+, and Al3+ ions. To explore the formation of such states in the aqueous phase, liquid-jet photoemission spectroscopy is employed. Using the core-hole-clock method, based on Auger–Meitner (AM) decay upon 1s excitation or ionization of the respective ions, upper limits are estimated for the metal-atom electron delocalization times to the neighboring water molecules. These delocalization processes represent the first steps in the formation of hydrated electrons, which are determined to take place on a timescale ranging from several hundred attoseconds (as) below the 1s ionization threshold to only 20 as far above the 1s ionization threshold. The decrease in the delocalization times as a function of the photon energy is continuous. This indicates that the excited electrons remain in the vicinity of the studied ions even above the ionization threshold, i.e., metal-ion electronic resonances associated with the CTTS state manifolds are formed. The three studied isoelectronic ions exhibit quantitative differences in their electron energetics and delocalization times, which are linked to the character of the respective excited states.

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Attosecond-pump attosecond-probe x-ray spectroscopy of liquid water

Cited by 24 publications

References 72 publications

The Physics of Water

The Physics of Water

Current Status of the MB-pol Data-Driven Many-Body Potential for Predictive Simulations of Water Across Different Phases

Attosecond formation of charge-transfer-to-solvent states of aqueous ions probed using the core-hole-clock technique

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