Lanthanide transport in angstrom-scale MoS2-based two-dimensional channels.

Rare earth elements (REEs), critical to modern industry, are difficult to separate and purify, given their similar physicochemical properties originating from the lanthanide contraction. Here, we systematically study the transport of lanthanide ions (Ln3+) in artificially confined angstrom-scale two-dimensional channels using MoS2-based building blocks in an aqueous environment. The results show that the uptake and permeability of Ln3+ assume a well-defined volcano shape peaked at Sm3+. This transport behavior is rooted from the tradeoff between the barrier for dehydration and the strength of interactions of lanthanide ions in the confinement channels, reminiscent of the Sabatier principle. Molecular dynamics simulations reveal that Sm3+, with moderate hydration free energy and intermediate affinity for channel interaction, exhibit the smallest dehydration degree, consequently resulting in the highest permeability. Our work not only highlights the distinct mass transport properties under extreme confinement but also demonstrates the potential of dialing confinement dimension and chemistry for greener REEs separation.

Anomalously enhanced ion transport and uptake in functionalized angstrom-scale two-dimensional channels.

Emulating angstrom-scale dynamics of the highly selective biological ion channels is a challenging task. Recent work on angstrom-scale artificial channels has expanded our understanding of ion transport and uptake mechanisms under confinement. However, the role of chemical environment in such channels is still not well understood. Here, we report the anomalously enhanced transport and uptake of ions under confined MoS2-based channels that are ~five angstroms in size. The ion uptake preference in the MoS2-based channels can be changed by the selection of surface functional groups and ion uptake sequence due to the interplay between kinetic and thermodynamic factors that depend on whether the ions are mixed or not prior to uptake. Our work offers a holistic picture of ion transport in 2D confinement and highlights ion interplay in this regime.

Vibrational Probe at the Electrochemical Interface: Dependence on Plasmon Coupling and Potential of the Lineshape in Two-Dimensional Infrared Spectroscopy.

Two-dimensional infrared spectroscopy of vibrational probes at an electrode surface shows promise for studying the structural dynamics at an active electrochemical interface. This interface is a complex environment where the solution structures in response to the applied potential. A strategy for achieving the necessary monolayer sensitivity is to use a plasmonically active electrode, which enhances the electromagnetic fields that produce the spectroscopic response. Here, we show how the coupling between the plasmon and the vibrations of the molecular monolayer impacts the FTIR and 2D IR spectroscopy, with an emphasis on the electrochemical potential difference spectra. We show how mixing between the vibrational and plasmonic states gives rise to the distortions that are observed in these measurements. This provides an important step toward 2D IR measurements of vibrational probes at the electrochemical interface as a tool for probing the structural dynamics in the double layer.

Development and Characterization of Electrodes for Surface-Specific Attenuated Total Reflection Two-Dimensional Infrared Spectroelectrochemistry.

Electrochemical interfaces still have remaining mysteries surrounding the interfacial region of the electrical double layer, despite being prevalent throughout the energy and water remediation industries. The electrical double layer is where many important dynamic processes such as catalysis and electron transfer occur. The goal of this work is to study the electrical double layer with two-dimensional infrared (2D IR) spectroscopy to experimentally access the details of the structural dynamics of this complex environment. However, there are several experimental challenges to applying 2D IR spectroscopy to this application, such as assuring the surface specificity of the spectrum, optimizing the signal strength while minimizing spectral distortions from dispersion and Fano line shapes, and selecting electrode materials that are both sufficiently IR compatible and conductive. Here we will discuss various considerations when designing 2D IR experiments of electrode interfaces utilizing several substrates and experimental configurations and demonstrate a robust method for 2D IR experiments of electrode interfaces under applied potential that combines nonconducting Si ATR wafers with conductive ITO and thin nanostructured films of plasmonically active Au functionalized with 3-mercapto-2-butanone (MCB). We show that layered electrodes on thin Si ATR wafers with MCB are sensitive to applied potential and that the distortions in the linear and 2D IR spectra are heavily dependent on the morphology of the Au surface.

Strong H-bonding from Zeolite BroÌ·nsted Acid Site to Water: Origin of the Broad IR Doublet.

Hydrogen bonding between water molecules and zeolite BroÌ·nsted acid sites (BAS) has received much attention due to the significant influence of water on the adsorption and catalytic properties of these widely used porous materials. When a single water molecule is adsorbed at the BAS, the zeolite O-H stretch vibration decreases in frequency and splits into two extraordinarily broad bands peaked near 2500 and 2900 cm-1 in the infrared (IR) spectrum. This broad doublet feature is the predominant IR signature used to identify and interpret water-BAS H-bonding at low hydration levels, but the origin of the band splitting is not well understood. In this study, we used broadband two-dimensional infrared (2D IR) spectroscopy to investigate zeolite HZSM-5 prepared with a single water molecule per BAS. We find that the 2D IR spectrum is not explained by the most common interpretation of Fermi resonance coupling between the stretch and the bend of the BAS OH group, which predicts intense excited-state transitions that are absent from the experimental results. We present an alternative model of a double-well proton stretch potential, where the band splitting is caused by excited-state tunneling through the proton-transfer barrier. This one-dimensional model reproduces the basic experimental pattern of transition frequencies and amplitudes, suggesting that the doublet bands may originate from a highly anharmonic potential in which the excited state proton wave functions are delocalized over the H-bond between zeolite BAS and adsorbed H2O. Additional details about molecular orientation and coordination of the adsorbed water molecule are also resolved in the 2D IR spectroscopy.

Amplification of mid-IR continuum for broadband 2D IR spectroscopy.

We report the generation and characterization of microjoule level, broad bandwidth femtosecond pulses in the mid-infrared (MIR) using optical parametric amplification of continuum MIR seed pulses in GaSe. The signal (3 µm) and idler (6 µm) pulses have energies of 6 µJ and 3 µJ with bandwidths of ∼950 cm-1 and 650 cm-1 FWHM and pulse lengths of 34 fs and 80 fs. Broadband 2D IR spectra of O-H and N-H transitions are acquired with the signal beam demonstrating the capabilities of this source for cross peak and line shape measurements.

From Networked to Isolated: Observing Water Hydrogen Bonds in Concentrated Electrolytes with Two-Dimensional Infrared Spectroscopy.

Superconcentrated electrolytes have emerged as a promising class of materials for energy storage devices, with evidence that high voltage performance is possible even with water as the solvent. Here, we study the changes in the water hydrogen bonding network induced by the dissolution of lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in concentrations ranging from the dilute to the superconcentrated regimes. Using time-resolved two-dimensional infrared spectroscopy, we observe the progressive disruption of the water-water hydrogen bond network and the appearance of isolated water molecules interacting only with ions, which can be identified and spectroscopically isolated through the intermolecular cross-peaks between the water and the TFSI- ions. Analyzing the vibrational relaxation of excitations of the H2O stretching mode, we observe a transition in the dominant relaxation path as the bulk-like water vanishes and is replaced by ion-solvation water with the rapid single-step relaxation of delocalized stretching vibrations into the low frequency modes being replaced by multistep relaxation through the intramolecular H2O bend and into the TFSI- high frequency modes prior to relaxing to the low frequency structural degrees of freedom. These results definitively demonstrate the absence of vibrationally bulk-like water in the presence of high concentrations of LiTFSI and especially in the superconcentrated regime, while additionally revealing aspects of the water hydrogen bond network that have been difficult to discern from the vibrational spectroscopy of the neat liquid.

Exchange-Mediated Transport in Battery Electrolytes: Ultrafast or Ultraslow?

Understanding the mechanisms of charge transport in batteries is important for the rational design of new electrolyte formulations. Persistent questions about ion transport mechanisms in battery electrolytes are often framed in terms of vehicular diffusion by persistent ion-solvent complexes versus structural diffusion through the breaking and reformation of ion-solvent contacts, i.e., solvent exchange events. Ultrafast two-dimensional (2D) IR spectroscopy can probe exchange processes directly via the evolution of the cross-peaks on picosecond time scales. However, vibrational energy transfer in the absence of solvent exchange gives rise to the same spectral signatures, hiding the desired processes. We employ 2D IR on solvent resonances of a mixture of acetonitrile isotopologues to differentiate chemical exchange and energy-transfer dynamics in a comprehensive series of Li+, Mg2+, Zn2+, Ca2+, and Ba2+ bis(trifluoromethylsulfonyl)imide electrolytes from the dilute to the superconcentrated regime. No exchange phenomena occur within at least 100 ps, regardless of the ion identity, salt concentration, and presence of water. All of the observed spectral dynamics originate from the intermolecular energy transfer. These results place the lower experimental boundary on the ion-solvent residence times to several hundred picoseconds, much slower than previously suggested. With the help of MD simulations and conductivity measurements on the Li+ and Zn2+ systems, we discuss these results as a continuum of vehicular and structural modalities that vary with concentration and emphasize the importance of collective electrolyte motions to ion transport. These results hold broadly applicable to many battery-relevant ions and solvents.

Characterization of Acetonitrile Isotopologues as Vibrational Probes of Electrolytes.

Acetonitrile has emerged as a solvent candidate for novel electrolyte formulations in metal-ion batteries and supercapacitors. It features a bright local C≡N stretch vibrational mode whose infrared (IR) signature is sensitive to battery-relevant cations (Li+, Mg2+, Zn2+, Ca2+) both in pure form and in the presence of water admixture across a full possible range of concentrations from the dilute to the superconcentrated regime. Stationary and time-resolved IR spectroscopy thus emerges as a natural tool to study site-specific intermolecular interactions from the solvent perspective without introducing an extrinsic probe that perturbs solution morphology and may not represent the intrinsic dynamics in these electrolytes. The metal-coordinated acetonitrile, water-separated metal-acetonitrile pair, and free solvent each have a distinct vibrational signature that allows their unambiguous differentiation. The IR band frequency of the metal-coordinated acetonitrile depends on the ion charge density. To study the ion transport dynamics, it is necessary to differentiate energy-transfer processes from structural interconversions in these electrolytes. Isotope labeling the solvent is a necessary prerequisite to separate these processes. We discuss the design principles and choice of the CD313CN label and characterize its vibrational spectroscopy in these electrolytes. The Fermi resonance between 13C≡N and C-D stretches complicates the spectral response but does not prevent its effective utilization. Time-resolved two-dimensional (2D) IR spectroscopy can be performed on a mixture of acetonitrile isotopologues and much can be learned about the structural dynamics of various species in these formulations.

Lineshape Distortions in Internal Reflection Two-Dimensional Infrared Spectroscopy: Tuning across the Critical Angle.

Reflection mode two-dimensional infrared spectroscopy (R-2DIR) has recently emerged as a tool that expands the utility of ultrafast IR spectroscopy toward a broader class of materials. The impact of experimental configurations on the potential distortions of the transient reflectance (TR) spectra has not been fully explored, particularly in the vicinity of the critical angle θc and through the crossover from total internal reflection to partial reflection. Here we study the impact on the spectral lineshape of a dilute bulk solution as θc is varied across the incident angle by tuning the refractive index of the solvent. We demonstrate the significance of several distortions, including the appearance of phase twisted lineshapes and apparent changes in the spectral inhomogeneity, and show how these distortions impact the interpretation of the TR and R-2DIR spectroscopies.

Structural Characterization of Protonated Water Clusters Confined in HZSM-5 Zeolites.

A molecular description of the structure and behavior of water confined in aluminosilicate zeolite pores is a crucial component for understanding zeolite acid chemistry under hydrous conditions. In this study, we use a combination of ultrafast two-dimensional infrared (2D IR) spectroscopy and ab initio molecular dynamics (AIMD) to study H2O confined in the pores of highly hydrated zeolite HZSM-5 (∼13 and ∼6 equivalents of H2O per Al atom). The 2D IR spectrum reveals correlations between the vibrations of both terminal and H-bonded O-H groups and the continuum absorption of the excess proton. These data are used to characterize the hydrogen-bonding network within the cluster by quantifying single-, double-, and non-hydrogen-bond donor water molecules. These results are found to be in good agreement with the statistics calculated from an AIMD simulation of an H+(H2O)8 cluster in HZSM-5. Furthermore, IR spectral assignments to local O-H environments are validated with DFT calculations on clusters drawn from AIMD simulations. The simulations reveal that the excess charge is detached from the zeolite and resides near the more highly coordinated water molecules in the cluster. When they are taken together, these results unambiguously assign the complex IR spectrum of highly hydrated HZSM-5, providing quantitative information on the molecular environments and hydrogen-bonding topology of protonated water clusters under extreme confinement.

Advanced Materials for Energy-Water Systems: The Central Role of Water/Solid Interfaces in Adsorption, Reactivity, and Transport.

The structure, chemistry, and charge of interfaces between materials and aqueous fluids play a central role in determining properties and performance of numerous water systems. Sensors, membranes, sorbents, and heterogeneous catalysts almost uniformly rely on specific interactions between their surfaces and components dissolved or suspended in the water-and often the water molecules themselves-to detect and mitigate contaminants. Deleterious processes in these systems such as fouling, scaling (inorganic deposits), and corrosion are also governed by interfacial phenomena. Despite the importance of these interfaces, much remains to be learned about their multiscale interactions. Developing a deeper understanding of the molecular- and mesoscale phenomena at water/solid interfaces will be essential to driving innovation to address grand challenges in supplying sufficient fit-for-purpose water in the future. In this Review, we examine the current state of knowledge surrounding adsorption, reactivity, and transport in several key classes of water/solid interfaces, drawing on a synergistic combination of theory, simulation, and experiments, and provide an outlook for prioritizing strategic research directions.

Water-in-Salt LiTFSI Aqueous Electrolytes. 1. Liquid Structure from Combined Molecular Dynamics Simulation and Experimental Studies.

The concept of water-in-salt electrolytes was introduced recently, and these systems have been successfully applied to yield extended operation voltage and hence significantly improved energy density in aqueous Li-ion batteries. In the present work, results of X-ray scattering and Fourier-transform infrared spectra measurements over a wide range of temperatures and salt concentrations are reported for the LiTFSI (lithium bis(trifluoromethane sulfonyl)imide)-based water-in-salt electrolyte. Classical molecular dynamics simulations are validated against the experiments and used to gain additional information about the electrolyte structure. Based on our analyses, a new model for the liquid structure is proposed. Specifically, we demonstrate that at the highest LiTFSI concentration of 20 m the water network is disrupted, and the majority of water molecules exist in the form of isolated monomers, clusters, or small aggregates with chain-like configurations. On the other hand, TFSI- anions are connected to each other and form a network. This description is fundamentally different from those proposed in earlier studies of this system.

Crossover from hydrogen to chemical bonding.

Hydrogen bonds (H-bonds) can be interpreted as a classical electrostatic interaction or as a covalent chemical bond if the interaction is strong enough. As a result, short strong H-bonds exist at an intersection between qualitatively different bonding descriptions, with few experimental methods to understand this dichotomy. The [F-H-F]- ion represents a bare short H-bond, whose distinctive vibrational potential in water is revealed with femtosecond two-dimensional infrared spectroscopy. It shows the superharmonic behavior of the proton motion, which is strongly coupled to the donor-acceptor stretching and disappears on H-bond bending. In combination with high-level quantum-chemical calculations, we demonstrate a distinct crossover in spectroscopic properties from conventional to short strong H-bonds, which identify where hydrogen bonding ends and chemical bonding begins.

Temperature-Jump 2D IR Spectroscopy with Intensity-Modulated CW Optical Heating.

Pulsed temperature-jump (T-jump) spectroscopy with infrared (IR) detection has been widely used to study biophysical processes occurring from nanoseconds to ∼1 ms with structural sensitivity. However, many systems exhibit structural dynamics on time scales longer than the millisecond barrier that is set by the time scale for thermal relaxation of the sample. We developed a linear and nonlinear infrared spectrometer coupled to an intensity-modulated continuous wave (CW) laser to probe T-jump-initiated chemical reactions from <1 ms to seconds. Time-dependent modulation of the CW laser leads to a <1 ms heating time as well as a constant final temperature (±3%) for the duration of the heating time. Temperature changes of up to 75 °C in D2O are demonstrated, allowing for nonequilibrium measurements inaccessible to standard pulsed optical T-jump setups. T-jump linear absorption, pump-probe, and two-dimensional IR (2D IR) spectroscopy are applied to the unfolding and refolding of ubiquitin and a model intercalated motif (i-motif) DNA sequence, and analysis of the observed signals is used to demonstrate the limits and utility of each method. Overall, the ability to probe temperature-induced chemical processes from <1 ms to many seconds with 2D IR spectroscopy provides multiple new avenues for time-dependent spectroscopy in chemistry and biophysics.

Vibrational Probe of Aqueous Electrolytes: The Field Is Not Enough.

In this work, we study the vibrational solvatochromism and dynamics of dilute acetone as a carbonyl probe in simple aqueous electrolytes as a function of salt composition and concentration. We observe a linear dependence of the redshift of the CO stretch mode as a function of concentration for each salt, with the magnitude of the effect scaling with the charge densities of the cations. Using molecular dynamics (MD) simulations, we compare the observed spectral shifts with the electrostatic field distributions imparted on the acetone O, comparing a fixed-charge model and a polarizable model, and find that the experimentally observed frequencies scale linearly with the electric field for a given salt, but there remains a substantial component of the solvatochromism that depends on the identity of the cation and apparently cannot be explained by the electrostatic fields alone. Finally, we use ultrafast 2D IR spectroscopy to study the salt dependence of the solvation dynamics. We observe an anomalous nonmonotonic dependence of the time scale of the dynamics on the salt concentration, which cannot be reproduced by the fluctuations in the electrostatic field determined from MD simulations. These results point to the importance of both electrostatic and nonelectrostatic effects in the vibrational solvatochromism and dynamics in this apparently simple model system.

Entropic barriers in the kinetics of aqueous proton transfer.

Aqueous proton transport is uniquely rapid among aqueous processes, mediated by fluctuating hydrogen bond reorganization in liquid water. In a process known as Grotthuss diffusion, the excess charge diffuses primarily by sequential proton transfers between water molecules rather than standard Brownian motion, which explains the anomalously high electrical conductivity of acidic solutions. Employing ultrafast IR spectroscopy, we use the orientational anisotropy decay of the bending vibrations of the hydrated proton complex to study the picosecond aqueous proton transfer kinetics as a function of temperature, concentration, and counterion. We find that the orientational anisotropy decay exhibits Arrhenius behavior, with an apparent activation energy of 2.4 kcal/mol in 1M and 2M HCl. Interestingly, acidic solutions at high concentration with longer proton transfer time scales display corresponding decreases in activation energy. We interpret this counterintuitive trend by considering the entropic and enthalpic contributions to the activation free energy for proton transfer. Halide counteranions at high concentrations impose entropic barriers to proton transfer in the form of constraints on the solution's collective H-bond fluctuations and obstruction of potential proton transfer pathways. The corresponding proton transfer barrier decreases due to weaker water-halide H-bonds in close proximity to the excess proton, but the entropic effects dominate and result in a net reduction in the proton transfer rate. We estimate the activation free energy for proton transfer as ∼1.0 kcal/mol at 280 K.

High-Level VSCF/VCI Calculations Decode the Vibrational Spectrum of the Aqueous Proton.

The hydrated excess proton is a common species in aqueous chemistry, which complexes with water in a variety of structures. The infrared spectrum of the aqueous proton is particularly sensitive to this array of structures, which manifests as continuous IR absorption from 1000 to 3000 cm-1 known as the "proton continuum". Because of the extreme breadth of the continuum and strong anharmonicity of the involved vibrational modes, this spectrum has eluded straightforward interpretation and simulation. Using protonated water hexamer clusters from reactive molecular dynamics trajectories, and focusing on their central H+(H2O)2 structures' spectral contribution, we reproduce the linear IR spectrum of the aqueous proton with a high-level local monomer quantum method and highly accurate many-body potential energy surface. The accuracy of this approach is first verified in the vibrational spectra of the two isomers of the protonated water hexamer in the gas phase. We then apply this approach to 800 H+(H2O)6 clusters, also written as [H+(H2O)2](H2O)4, drawn from multistate empirical valence bond simulations of the bulk liquid to calculate the infrared spectrum of the aqueous proton complex. Incorporation of anharmonic effects to the vibrational potential and quantum mechanical treatment of the proton produces a better agreement to the infrared spectrum compared to that of the double-harmonic approximation. We assess the correlation of the proton stretching mode with different atomistic coordinates, finding the best correlation with ⟨ROH⟩, the expectation value of the proton-oxygen distance ROH. We also decompose the IR spectrum based on normal mode vibrations and ⟨ROH⟩ to provide insight on how different frequency regions in the continuum report on different configurations, vibrational modes, and mode couplings.

Two-dimensional electronic vibrational spectroscopy and ultrafast excitonic and vibronic photosynthetic energy transfer.

Two-dimensional electronic-vibrational (2DEV) spectroscopy is a new coherent spectroscopic technique, which shows considerable promise for unravelling complex molecular dynamics. In this Discussion we describe an application to the energy transfer pathway in the major light harvesting protein, LHCII, providing new data on the center line slopes (CLS) of the spectral peaks. The CLS provides information that appears unique to the 2DEV method. We then outline a general approach to calculating 2DEV spectra which is valid for strongly and weakly coupled molecular systems. We conclude with some prospects for the future development of 2DEV spectroscopy and its theoretical analysis.