Bridging the concepts of homogeneous and heterogeneous reactions is an important challenge in modern chemistry. Toward that end, here, we connect the homogeneous chemistry concept of the Hammett parameter, used by organic and organometallic chemists to quantify the electron-withdrawing capability of a functional group, to the electrochemical concept of polarization induced by a biased electrode. Because these two effects share similar origins, a theoretically motivated and experimentally verifiable link between them can be established. A convenient experiment that links the two is measuring the shift of vibrational frequency that is induced by these factors. To achieve this, first, we have measured the vibrational frequency of the nitrile stretch of 4-R-benzonitrile for a series of functional groups R spanning the Hammett parameter range −0.83 ≤ σp ≤ +1.11. Because the nitrile stretch is sensitive to molecular polarization, its frequency depends on the Hammett parameter of the polarizing functional groups. Second, we have measured the nitrile vibrational frequency of 4-mercaptobenzonitrile tethered on a gold electrode and polarized in an electrochemical cell as a function of potential from −1.4 to +0.6 V versus Ag/AgCl. Comparison of the nitrile-stretch frequency between the two experiments allows us to correlate the polarization caused by a functional group to that induced by the electrode. The data suggest equivalence between the Hammett parameter σp and the local electric field at the electrode interface, therefore allowing a polarizing electrode to be treated as a functional group. Computational work supports the experimental results and allows for a quantitative relation between the interfacial electric field and σp. We anticipate the benefits of this correlation, in particular, in linking concepts between homogeneous and heterogeneous reactions.

A time-dependent change in the refractive index of a material leads to a change in the frequency of an optical beam passing through that medium. Here, we experimentally demonstrate that this effectknown as adiabatic frequency conversion (AFC)can be significantly enhanced by a nonlinear epsilon-near-zero-based (ENZ-based) plasmonic metasurface. Specifically, by using a 63-nm-thick metasurface, we demonstrate a large, tunable, and broadband frequency shift of up to ∼11.2 THz with a pump intensity of 4 GW/ cm 2 . Our results represent a decrease of ∼10 times in device thickness and 120 times in pump peak intensity compared with the cases of bare, thicker ENZ materials for the similar amount of frequency shift. Our findings might potentially provide insights for designing efficient time-varying metasurfaces for the manipulation of ultrafast pulses.

Understanding ionic structure and electrostatic environments near a surface has both fundamental and practical value. In electrochemistry, especially when room temperature ionic liquids (ILs) are involved, the complex ionic structure near the interface is expected to crucially influence reactions. Here we report evidence that even in dilute aqueous solutions of several ILs, the ions aggregate near the surface in ways that are qualitatively different from simple electrolytes. We have used a vibrational probe molecule, 4-mercapto­benzonitrile (MBN), tethered to a metal surface to monitor the behavior of the ionic layers. The characteristic nitrile vibrational frequency of this molecule has distinct values in the presence of pure water (∼2232 cm–1) and pure IL (for example, ∼2226 cm–1 for ethylmethyl­imidazolium tetrafluoroborate, [EMIM]­[BF4]). This difference reflects the local electrostatic field and the hydrogen-bonding variations between these two limiting cases. We tracked this frequency shift as a function of IL concentration in water all the way from pure water to pure IL. We report two important findings. First, only one nitrile peak is observed for the entire concentration range, indicating that at least on the length scale of the probe molecule water and ILs do not phase separate within the interface, and no heterogeneously distinct electrostatic environments are formed. Second, and more importantly, we find that even up to a significant mole fraction of bulk water (x ∼ 0.95), the nitrile frequency does not change from that indicative of a pure IL for [EMIM]­[BF4], indicating preferential aggregation of the ions near the surface. Because this behavior is very similar to surfactants, we chose an imidazolium cation with a longer side chain which resulted in behavior expected from a surfactant, with a preferential layer of the ions on the surface even in dilute water solutions (x ∼ 0.995). This observation indicates that even those ILs that are not nominally categorized as surfactants have a strong tendency to aggregate at the surface. Because ILs serve as electrolytes in a range of electrochemical reactions, including those requiring water, our results are likely useful for mechanistic understanding and tuning of such reactions.

Most electrochemical reactions require delivery of protons, often from water, to surface-adsorbed species. However, water also acts as a competitor to many such processes by directly reacting with the electrode, which necessitates using water in small amounts. Controlling the water content and structure near the surface is an important frontier in directing the reactivity and selectivity of electrochemical reactions. Surfactants accumulate near surfaces, and therefore, they can be used as agents to control interfacial water. Using mid-IR spectroelectrochemistry, we show that a modest concentration (1 mM) of the cationic surfactant CTAB in mixtures of 10 M water in an organic solvent (dDMSO) has a large effect on the interfacial water concentration, changing it by up to ∼35% in the presence of an applied potential. The major cause of water content change is displacement due to the accumulation or depletion of surfactants driven by potential. Two forces drive the surfactants to the electrode: the applied potential and the hydrophobic interactions with the water in the bulk. We have quantified their competition by varying the water content in the bulk. To our knowledge, for the first time, we have identified the electrochemical equivalent of the hydrophobic drive. For our system, a change in applied potential of 1 V has the same effect as adding a 0.55 mole fraction of water to the bulk. This work illustrates the significance of surfactants in the partitioning of water between the bulk and the surface and paves the way toward engineering interfacial water structures for controlling electrochemical reactions.

Ionic liquids (ILs) have both fundamental and practical value in interfacial science and electrochemistry. However, understanding their behavior near a surface is challenging because of strong Coulomb interactions and large and irregular ionic sizes, which affect both their structure and energetics. To understand this problem, we present a combined experimental and computational study using a vibrational probe molecule, 4-mercaptobenzonitrile, inserted at the junction between a metal and a variety of ILs. The vibrational frequency of the nitrile in the probe molecule reports on the local solvation environment and the electrostatic field at this junction. Within the ethylmethyl imidazolium (EMIM + ) cation family of ILs, we varied the anions over a range of sizes and types. Complementing our surface spectroscopy, we also ran molecular dynamics simulations of these interfaces to better understand the ionic structures that produced the measured fields. The magnitude of the frequency shifts, and thereby fields, shows a general correlation with the size of anions, with larger anions corresponding to smaller fields. We find that the source of this correlation is partial intercalation of smaller anions into the probe monolayer, resulting in tighter packing of ionic layers near the surface. Larger anions reduce the overall lateral ion packing density near the surface, which reduces the net charge per unit area and explains the smaller observed fields. The insight from this work is important for developing a fundamental picture of concentrated electrolytes near interfaces and can help with designing ILs to create tailored electric fields near an electrode.