The distribution of ions at the air/water interface plays a decisive role in many natural processes. Several studies have reported that larger ions tend to be surface-active, implying ions are located on top of the water surface, thereby inducing electric fields that determine the interfacial water structure. Here we challenge this view by combining surface-specific heterodyne-detected vibrational sum-frequency generation with neural network-assisted ab initio molecular dynamics simulations. Our results show that ions in typical electrolyte solutions are, in fact, located in a subsurface region, leading to a stratification of such interfaces into two distinctive water layers. The outermost surface is ion-depleted, and the subsurface layer is ion-enriched. This surface stratification is a key element in explaining the ion-induced water reorganization at the outermost air/water interface.

Atomic-scale simulations have progressed tremendously over the past decade, largely thanks to the availability of machine-learning interatomic potentials. These potentials combine the accuracy of electronic structure calculations with the ability to reach extensive length and time scales. The i-PI package facilitates integrating the latest developments in this field with advanced modeling techniques thanks to a modular software architecture based on inter-process communication through a socket interface. The choice of Python for implementation facilitates rapid prototyping but can add computational overhead. In this new release, we carefully benchmarked and optimized i-PI for several common simulation scenarios, making such overhead negligible when i-PI is used to model systems up to tens of thousands of atoms using widely adopted machine learning interatomic potentials, such as Behler–Parinello, DeePMD, and MACE neural networks. We also present the implementation of several new features, including an efficient algorithm to model bosonic and fermionic exchange, a framework for uncertainty quantification to be used in conjunction with machine-learning potentials, a communication infrastructure that allows for deeper integration with electronic-driven simulations, and an approach to simulate coupled photon-nuclear dynamics in optical or plasmonic cavities.

We address the double hydrogen transfer (DHT) dynamics of the porphycene molecule, a complex paradigmatic system in which the making and breaking of H-bonds in a highly anharmonic potential energy surface require a quantum mechanical treatment not only of the electrons but also of the nuclei. We combine density functional theory calculations, employing hybrid functionals and van der Waals corrections, with recently proposed and optimized path-integral ring-polymer methods for the approximation of quantum vibrational spectra and reaction rates. Our full-dimensional ring-polymer instanton simulations show that below 100 K the concerted DHT tunneling pathway dominates but between 100 and 300 K there is a competition between concerted and stepwise pathways when nuclear quantum effects are included. We obtain ground-state reaction rates of 2.19 × 10¹¹ s^–1 at 150 K and 0.63 × 10¹¹ s^–1 at 100 K, in good agreement with experiment. We also reproduce the puzzling N–H stretching band of porphycene with very good accuracy from thermostated ring-polymer molecular dynamics simulations. The position and line shape of this peak, centered at around 2600 cm^–1 and spanning 750 cm^–1, stem from a combination of very strong H-bonds, the coupling to low-frequency modes, and the access to cis-like isomeric conformations, which cannot be appropriately captured with classical-nuclei dynamics. These results verify the appropriateness of our general theoretical approach and provide a framework for a deeper physical understanding of hydrogen transfer dynamics in complex systems.

Water molecules adsorbed on inorganic substrates play an important role in several technological applications. In the presence of light atoms in adsorbates, nuclear quantum effects (NQEs) influence the structural stability and the dynamical properties of these systems. In this work, we explore the impact of NQEs on the dissociation of water wires on stepped Pt(221) surfaces. By performing ab initio molecular dynamics simulations with van der Waals corrected density functional theory, we note that several competing minima for both intact and dissociated structures are accessible at finite temperatures, making it important to assess whether harmonic estimates of the quantum free energy are sufficient to determine the relative stability of the different states. We thus perform ab initio path integral molecular dynamics (PIMD) in order to calculate these contributions taking into account the conformational entropy and anharmonicities at finite temperatures. We propose that when adsorption is weak and NQEs on the substrate are negligible, PIMD simulations can be performed through a simple partition of the system, resulting in considerable computational savings. We then calculate the full contribution of NQEs to the free energies, including also anharmonic terms. We find that they result in an increase of up to 20% of the quantum contribution to the dissociation free energy compared with the harmonic estimates. We also find that the dissociation process has a negligible contribution from tunneling but is dominated by zero point energies, which can enhance the rate of dissociation by three orders of magnitude. Finally we highlight how both temperature and NQEs indirectly impact dipoles and the redistribution of electron density, causing work function changes of up to 0.4 eV with respect to static estimates. This quantitative determination of the change in the work function provides a possible approach to determine experimentally the most stable configurations of water oligomers on the stepped surfaces.

The response of water to electric fields is critical to the performance and stability of electrochemical devices, and the selectivity of enzymatic, atmospheric, and organic reactions. A key process in this context is the water (auto)dissociation reaction (WD), which governs acid-base aqueous chemistry and shapes reaction rates and mechanisms. Despite its significance, the thermodynamics of the WD reaction in electrified environments remains poorly understood. Here, we investigate the WD reaction under external electric fields using ab initio molecular dynamics simulations within the framework of the modern theory of polarization. Our results reveal that strong electric fields dramatically enhance the WD reaction, increasing the equilibrium constant by several orders of magnitude. Moreover, we show that the applied field transforms the WD reaction from an entropically hindered process to an entropy-driven one. Analysis shows that this is because the electric field alters the tendency of ions to be structure makers or structure breakers. By highlighting how strong electric fields reshape solvent organization and reactivity, this work opens new avenues for designing aqueous electro-catalysts that leverage solvent entropy to enhance their performance.