Robert E. Grisenti

The fate of a metastable substance is governed by rare nucleation events, whose full microscopic details still remain elusive despite over 150 years of study. Experimental nucleation rates often differ by many orders of magnitude from theory and simulations, limiting predictive power. In this Perspective, after a general overview on nucleation, we focus on crystallization in three representative systems: metastable water, colloidal suspensions, and Lennard-Jones liquids. The latter, which are well realized by rare-gas liquids, provide a touchstone for nucleation theory. Recent femtosecond X-ray diffraction experiments on supercooled argon and krypton deliver accurate crystal nucleation statistics and direct insight into structural defects such as stacking faults. These advances establish rare-gas liquids as uniquely well-controlled systems bridging experiment, simulation, and theory, and pave the way toward a more complete microscopic understanding of nucleation.

We demonstrate an advanced scattering method for accessing the 3D reciprocal space of crystalline structures forming in a rapidly supercooled noble-gas liquid using a combination of femtosecond X-ray diffraction and X-ray cross-correlation analysis. The preservation of angular information from the scattering signal allows probing the structure factor along selected directions in reciprocal space and identifying signatures undetectable in azimuthally integrated scattering curves. Therefore, more information from serial diffraction experiments on stochastic crystallization processes can be retrieved despite the inherent variation of the crystal orientation and morphology for each single probe. We also demonstrate how different features in the correlation maps can be associated with certain forms of stacking faults, which enables studying such defects in situ and disentangling them from simultaneous changes in crystal size and temperature.

The liquid-to-solid phase transition is a complex process that is difficult to investigate experimentally with sufficient spatial and temporal resolution. A key aspect of the transition is the formation of a critical seed of the crystalline phase in a supercooled liquid, that is, a liquid in a metastable state below the melting temperature. This stochastic process is commonly described within the framework of classical nucleation theory, but accurate tests of the theory in atomic and molecular liquids are challenging. Here, we employ femtosecond x-ray diffraction from microscopic liquid jets to study crystal nucleation in supercooled liquids of the rare gases argon and krypton. Our results provide stringent limits to the validity of classical nucleation theory in atomic liquids, and offer the long-sought possibility of testing nonclassical extensions of the theory.

Quantum electrodynamics (QED), the quantum field theory that describes the interaction between light and matter, is commonly regarded as the best-tested quantum theory in modern physics. However, this claim is mostly based on extremely precise studies performed in the domain of relatively low field strengths and light atoms and ions^1–6. In the realm of very strong electromagnetic fields such as in the heaviest highly charged ions (with nuclear charge Z ≫ 1), QED calculations enter a qualitatively different, non-perturbative regime. Yet, the corresponding experimental studies are very challenging, and theoretical predictions are only partially tested. Here we present an experiment sensitive to higher-order QED effects and electron–electron interactions in the high-Z regime. This is achieved by using a multi-reference method based on Doppler-tuned X-ray emission from stored relativistic uranium ions with different charge states. The energy of the 1s_1/22p_3/2 J = 2 → 1s_1/22s_1/2 J = 1 intrashell transition in the heaviest two-electron ion (U⁹⁰⁺) is obtained with an accuracy of 37 ppm. Furthermore, a comparison of uranium ions with different numbers of bound electrons enables us to disentangle and to test separately the one-electron higher-order QED effects and the bound electron–electron interaction terms without the uncertainty related to the nuclear radius. Moreover, our experimental result can discriminate between several state-of-the-art theoretical approaches and provides an important benchmark for calculations in the strong-field domain.

Knowledge of the refractive index of water in the deeply supercooled metastable liquid state is important, for example, for an accurate description of optical reflection and refraction processes occurring in clouds. However, a measurement of both the temperature and wavelength dependence of the refractive index under such extreme conditions is challenging. Here, we employ Raman spectroscopy in combination with microscopic water jets in vacuum to obtain the refractive index of supercooled water to a lowest temperature of 230.3 K. While our approach is based on the analysis of Mie resonances in Raman spectra measured by using a single excitation wavelength at 532 nm, it allows us to obtain the refractive index in a wide visible wavelength range from 534 to 675 nm. Because of a direct link between the refractive index and density of water, our results provide a promising approach to help improve our understanding of water's anomalous behavior.

Crystallization is a fundamental process in materials science, providing the primary route for the realization of a wide range of new materials. Crystallization rates are also considered to be useful probes of glass-forming ability. At the microscopic level, crystallization is described by the classical crystal nucleation and growth theories, yet in general solid formation is a far more complex process. In particular, the observation of apparently different crystal growth regimes in many binary liquid mixtures greatly challenges our understanding of crystallization. Here, we study by experiments, theory and computer simulations the crystallization of supercooled mixtures of argon and krypton, showing that crystal growth rates in these systems can be reconciled with existing crystal growth models only by explicitly accounting for the non-ideality of the mixtures. Our results highlight the importance of thermodynamic aspects in describing the crystal growth kinetics, providing a substantial step towards a more sophisticated theory of crystal growth.