The molecular structure of water is dynamic, with intermolecular hydrogen (H) bond interactions being modified by both electronic charge transfer and nuclear quantum effects (NQEs). Electronic charge transfer and NQEs potentially change under acidic or basic conditions, but such details have not been measured. In this work, we developed correlated vibrational spectroscopy, a symmetry-based method that separates interacting from noninteracting molecules in self- and cross-correlation spectra, giving access to previously inaccessible information. We found that hydroxide (OH ⁻ ) donated ~8% more negative charge to the H bond network of water, and hydronium (H ₃ O ⁺ ) accepted ~4% less negative charge from the H bond network of water. Deuterium oxide (D ₂ O) had ~9% more H bonds compared with water (H ₂ O), and acidic solutions displayed more dominant NQEs than basic ones.

Whereas a broad range of literature exists on the spectroscopy of water in disparate conditions, infrared (IR) and Raman spectra of water subjected to electric fields have never extensively been investigated so far. Based on ab initio molecular dynamics simulations, here we present IR and Raman spectra of bulk liquid water under the effect of static electric fields. A contraction of the entire frequency range is recorded upon increasing the field intensity both in the IR and in the Raman spectra. Whilst the OH stretching band is progressively shifted toward lower frequencies – indicating a field-induced strengthening of the H-bond network – all the other bands are up-shifted by the field. Furthermore, an evident modification of the librational mode band appears in all the spectra. Finally, the order-maker action of the field emerges also from the increase of the water orientational tetrahedral order. Upon field exposure, the water structure becomes more “ice like”.

Water is routinely exposed to external electric fields. Whether, for example, at physiological conditions, in contact with biological systems, or at the interface of polar surfaces in countless technological settings, water responds to fields on the order of a few V Å⁻¹ in a manner that is under intense investigation. Dating back to the 19th century, the possibility of solidifying water upon applying electric fields – a process known as electrofreezing – is an alluring promise that has canalized major efforts since, with uncertain outcomes. Here, we perform long (up to 500 ps per field strength) ab initio molecular dynamics simulations of water at ambient conditions under external electric fields. We show that fields of 0.10 − 0.15 V Å⁻¹ induce electrofreezing to a ferroelectric amorphous phase which we term f-GW (ferroelectric glassy water). The transition occurs after ~ 150 ps for a field of 0.15 V Å⁻¹ and after ~ 200 ps for a field of 0.10 V Å⁻¹ and is signaled by a structural and dynamic arrest and the suppression of the fluctuations of the hydrogen bond network. Our work reports evidence of electrofreezing of bulk liquid water at ambient conditions and therefore impacts several fields, from fundamental chemical physics to biology and catalysis.

The reaction pathways connecting methanol to methane and formaldehyde are among the most emblematic in chemistry because of their outstanding interest in the fields of energy, synthesis, and bio- and geo-chemistry. Despite of its fundamental nature, the one-pot synthesis of formaldehyde and methane stemming from methanol has never been reported before. Here we present a study, based on ab initio molecular dynamics and free-energy methods, in which the simultaneous oxidation and reduction (i.e., the disproportionation) of liquid methanol into methane and formaldehyde has been achieved at ambient temperature through the application of a static electric field. Because strong electric fields can be generated in the proximity of field emitter tips, this finding shows that the challenge of experimentally disproportionating methanol into formaldehyde and methane could be attempted. We show that the methanol “solvent” molecules play a major role in this process and that the chemical pathway connecting methanol to the detected products in the bulk liquid phase is very different from its reproduced gas-phase counterpart. Finally, we demonstrate that switching on an external electric field drastically modifies the reaction network of methanol, lowering some activation barriers, stabilizing the methane and formaldehyde products, and opening otherwise difficult-to-achieve chemical routes.