The properties of the water network in concentrated HCl acid pools in nanometer-sized reverse nonionic micelles were probed with TeraHertz absorption, dielectric relaxation spectroscopy, and reactive force field simulations capable of describing proton hopping mechanisms. We identify that only at a critical micelle size of W₀ =9 do solvated proton complexes form in the water pool, accompanied by a change in mechanism from Grotthuss forward shuttling to one that favors local oscillatory hopping. This is due to a preference for H⁺ and Cl^- ions to adsorb to the micelle interface, together with an acid concentration effect that causes a "traffic jam" in which the short-circuiting of the hydrogen-bonding motif of the hydronium ion decreases the forward hopping rate throughout the water interior even as the micelle size increases. These findings have implications for atmospheric chemistry, biochemical and biophysical environments, and energy materials, as transport of protons vital to these processes can be suppressed due to confinement, aggregation, and/or concentration.

Transport mechanisms of solvated protons of 1 M HCl acid pools, confined within reverse micelles (RMs) containing the negatively charged surfactant sodium bis(2-ethylhexyl) sulfosuccinate (NaAOT) or the positively charged cetyltrimethylammonium bromide (CTABr), are analyzed with reactive force field simulations to interpret dynamical signatures from TeraHertz absorption and dielectric relaxation spectroscopy. We find that the forward proton hopping events for NaAOT are further suppressed compared to a nonionic RM, while the Grotthuss mechanism ceases altogether for CTABr. We attribute the sluggish proton dynamics for both charged RMs as due to headgroup and counterion charges that expel hydronium and chloride ions from the interface and into the bulk interior, thereby increasing the pH of the acid pools relative to the nonionic RM. For charged NaAOT and CTABr RMs, the localization of hydronium near a counterion or conjugate base reduces the Eigen and Zundel configurations that enable forward hopping. Thus, localized oscillatory hopping dominates, an effect that is most extreme for CTABr in which the proton residence time increases dramatically such that even oscillatory hopping is slow.

The photo-induced radiolysis of water is an elementary reaction in biology and chemistry, forming solvated electrons, OH radicals, and hydronium cations on fast time scales. Here, we use an optical-pump terahertz-probe spectroscopy setup to trigger the photoionization of water molecules with optical laser pulses at ~400 nm and then time-resolve the transient solvent response with broadband terahertz (THz) fields with a ~90 fs time resolution. We observe three distinct spectral responses. The first is a positive broadband mode that can be attributed to an initial diffuse, delocalized electron with a radius of (22 ± 1) Å, which is short lived (<200 fs) because the absorption is blue-shifting outside of the THz range. The second emerging spectroscopic signature with a lifetime of about 150 ps is attributed to an intermolecular mode associated with a mass rearrangement of solvent molecules due to charge separation of radicals and hydronium cations. After 0.2 ps, we observe a long-lasting THz signature with depleted intensity at 110 cm^-1 that is well reproduced by ab initio molecular dynamics. We interpret this negative band at 110 cm^-1 as the solvent cage characterized by a weakening of the hydrogen bond network in the first and second hydration shells of the cavity occupied by the localized electron.

Photo-induced excited-state proton transfer (ESPT) reactions are of central importance in many biological and chemical processes. Identifying mechanistic details of the solvent reorganizations that facilitate proton transfer however, is challenging for current experimental and theoretical approaches. Using optical pump THz probe (OPTP) spectroscopy and molecular dynamics simulations, we were able to elucidate the ultrafast changes in the solvation environment for three derivatives of pyranine: the photoacid HPTS, the methoxy derivative MPTS, and the photobase OPTS. Experimentally, we find damped oscillations in the THz signal at short times and our simulations enable their assignment to vibrational energy transfer beatings between the photoexcited chromophore and nearby solvent molecules. The simulations of HPTS reveal strikingly efficient sub-ps energy transfer into a particular solvent mode, that is active near 4 THz, and which can provide the requisite energy required for solvent reorganization promoting proton transfer. Similar oscillations are present in the THz signal for all three derivatives, however the signal is damped rapidly for HPTS (within 0.4 ps) and more slowly for MPTS (within 1.4 ps) and OPTS (within 2.0 ps). For HPTS, we also characterize an additional phonon-like propagation of the proton into the bulk with a 140 ps period and an 83 ps damping time. Thermalization of the solvent occurs on a time scale exceeding 120 ps.

Water under nanoconfinement at ambient conditions has exhibited low-dimensional ice formation and liquid-solid phase transitions, but with structural and dynamical signatures that map onto known regions of water's phase diagram. Using terahertz (THz) absorption spectroscopy and ab initio molecular dynamics, we have investigated the ambient water confined in a supramolecular tetrahedral assembly, and determined that a dynamically distinct network of 9 ± 1 water molecules is present within the nanocavity of the host. The low-frequency absorption spectrum and theoretical analysis of the water in the Ga₄L₆^12- host demonstrate that the structure and dynamics of the encapsulated droplet is distinct from any known phase of water. A further inference is that the release of the highly unusual encapsulated water droplet creates a strong thermodynamic driver for the high-affinity binding of guests in aqueous solution for the Ga₄L₆^12- supramolecular construct.

The double layer at the solid/electrolyte interface is a key concept in electrochemistry. Here, we present an experimental study combined with simulations, which provides a molecular picture of the double-layer formation under applied voltage. By THz spectroscopy we are able to follow the stripping away of the cation/anion hydration shells for an NaCl electrolyte at the Au surface when decreasing/increasing the bias potential. While Na⁺ is attracted toward the electrode at the smallest applied negative potentials, stripping of the Cl^- hydration shell is observed only at higher potential values. These phenomena are directly measured by THz spectroscopy with ultrabright synchrotron light as a source and rationalized by accompanying molecular dynamics simulations and electronic-structure calculations.