Controlling the Structure of MoS2 Membranes via Covalent Functionalization with Molecular Spacers.

Restacked two-dimensional (2D) materials represent a new class of membranes for water-ion separations. Understanding the interplay between the 2D membrane's structure and the constituent material's surface chemistry to its ion sieving properties is crucial for further membrane development. Here, we reveal, and tune via covalent functionalization, the structure of MoS2-based membranes. We find features on both the ∼1 nm (interlayer spacing) and ∼100 nm (mesoporous voids between layers) length scales that evolve with the hydration level. The functional groups act as permanent molecular spacers, preventing local impermeability caused by irreversible restacking and promoting the uniform rehydration of the membrane. Molecular dynamics simulations show that the choice of functional group tunes the structure of water within the MoS2 channel and consequently determines the hydrated interlayer spacing. We demonstrate that MoS2 membranes functionalized with acetic acid have consistently ∼92% rejection of Na2SO4 with a flux of ∼1.5 lm-2 hr-1 bar-1.

IR Spectroscopy Can Reveal the Mechanism of K+ Transport in Ion Channels.

Ion channels like KcsA enable ions to move across cell membranes at near diffusion-limited rates and with very high selectivity. Various mechanisms have been proposed to explain this phenomenon. Broadly, there is disagreement among the proposed mechanisms about whether ions occupy adjacent sites in the channel during the transport process. Here, using a mixed quantum-classical approach to calculate theoretical infrared spectra, we propose a set of infrared spectroscopy experiments that can discriminate between mechanisms with and without adjacent ions. These experiments differ from previous ones in that they independently probe specific ion binding sites within the selectivity filter. When ions occupy adjacent sites in the selectivity filter, the predicted spectra are significantly redshifted relative to when ions do not occupy adjacent sites. Comparisons between theoretical and experimental peak frequencies will therefore discriminate the mechanisms.

Modeling nonlocal electron-phonon coupling in organic crystals using interpolative maps: The spectroscopy of crystalline pentacene and 7,8,15,16-tetraazaterrylene.

Electron-phonon coupling plays a central role in the transport properties and photophysics of organic crystals. Successful models describing charge- and energy-transport in these systems routinely include these effects. Most models for describing photophysics, on the other hand, only incorporate local electron-phonon coupling to intramolecular vibrational modes, while nonlocal electron-phonon coupling is neglected. One might expect nonlocal coupling to have an important effect on the photophysics of organic crystals because it gives rise to large fluctuation in the charge-transfer couplings, and charge-transfer couplings play an important role in the spectroscopy of many organic crystals. Here, we study the effects of nonlocal coupling on the absorption spectrum of crystalline pentacene and 7,8,15,16-tetraazaterrylene. To this end, we develop a new mixed quantum-classical approach for including nonlocal coupling into spectroscopic and transport models for organic crystals. Importantly, our approach does not assume that the nonlocal coupling is linear, in contrast to most modern charge-transport models. We find that the nonlocal coupling broadens the absorption spectrum non-uniformly across the absorption line shape. In pentacene, for example, our model predicts that the lower Davydov component broadens considerably more than the upper Davydov component, explaining the origin of this experimental observation for the first time. By studying a simple dimer model, we are able to attribute this selective broadening to correlations between the fluctuations of the charge-transfer couplings. Overall, our method incorporates nonlocal electron-phonon coupling into spectroscopic and transport models with computational efficiency, generalizability to a wide range of organic crystals, and without any assumption of linearity.

Mid-IR spectroscopy of supercritical water: From dilute gas to dense fluid.

Mixed quantum-classical methods are commonly used to calculate infrared spectra for condensed-phase systems. These methods have been applied to study water in a range of conditions from liquid to solid to supercooled. Here, we show that these methods also predict infrared line shapes in excellent agreement with experiments in supercritical water. Specifically, we study the OD stretching mode of dilute HOD in H2O. We find no qualitative change in the spectrum upon passing through the near-critical region (Widom line) or the hydrogen-bond percolation line. At very low densities, the spectrum does change qualitatively, becoming rovibrational in character. We describe this rovibrational spectrum from the perspective of classical mechanics and provide a classical interpretation of the rovibrational line shape for both HOD and H2O. This treatment is perhaps more accessible than the conventional quantum-mechanical treatment.

Percolation in supercritical water: Do the Widom and percolation lines coincide?

Hydrogen bonding distinguishes water from simpler fluids. Here, we use classical molecular dynamics to study the percolation transition in the hydrogen bond network of supercritical water. We find that, contrary to some previous work, the percolation line in both the pressure-temperature and density-temperature planes does not coincide with the Widom line. This difference stems from a fundamental distinction between the Widom line, which is thermodynamic in nature, and the percolation transition, which depends only on connectivity. For example, we show that percolation-related quantities collapse onto master curves when plotted with respect to a measure of connectivity rather than thermodynamic variables. We then use the Galam-Mauger formula to understand the properties of the hydrogen bonding network. We find that the percolation transition in supercritical water can shed light on the hydrogen bonding network in room temperature liquid water.

Linear Response Theory for Water Transport Through Dry Nanopores.

Porous two-dimensional crystals like graphene have the potential to revolutionize reverse-osmosis membrane technology. The permeability is a common figure of merit that describes the ease with which water flows through a membrane. For two-dimensional crystals, the permeability can be orders of magnitude higher than it is in conventional reverse-osmosis membranes. We apply our Gaussian Dynamics nonequilibrium molecular dynamics simulation method to very hydrophobic two-dimensional membranes and find that the current-pressure drop relationship becomes nonlinear. In this regime, the conventional permeability is an inadequate descriptor of the passage process, and the transport mechanism becomes a two-step one. The backing pressure first causes the pore to wet, and after it reaches a threshold pressure, water transport takes place from the wet state. We recover a simple description of the transport process by applying linear response theory with respect to the wet reference state rather than the dry one. A macroscopic thermodynamic argument supports our mechanistic description and predicts the wetting threshold pressure as a function of the contact angle.

Dephasing and Decoherence in Vibrational and Electronic Line Shapes.

Absorption and emission line shapes of vibrational and electronic transitions in liquids are broadened by interactions with the "bath" (in this case, the rotational and translational degrees of freedom of all the molecules in the liquid). If these degrees of freedom are treated classically, the broadening process is often known as dephasing. If, on the other hand, the bath degrees of freedom are instead treated quantum mechanically, there is additional broadening due to what is known in the chemical-physics literature as decoherence. The question addressed in this paper is the relative importance of decoherence (bath quantum effects) and dephasing. We present general developments of this subject for absorption and emission line shapes, discover several new relationships connecting classical and quantum treatments of the bath, and also consider the Stokes shift (difference in peak frequencies in absorption and emission). We next draw some general conclusions by considering a model system whose transition-frequency time-correlation function has only one bath time scale. We then consider a realistic system of the vibrational OH stretch transition of dilute HOD in liquid D2O at room temperature. For this system, we conclude that bath quantum effects are not very important, except for the Stokes shift. More generally, we argue that this is the case for many vibrational and most electronic transitions in room-temperature liquids.

On the Nature of Trapped-Hole States in CdS Nanocrystals and the Mechanism of Their Diffusion.

Recent transient absorption experiments on CdS nanorods suggest that photoexcited holes rapidly trap to the surface of these particles and then undergo diffusion along the rod surface. In this Letter, we present a semiperiodic density functional theory model for the CdS nanocrystal surface, analyze it, and comment on the nature of both the hole-trap states and the mechanism by which the holes diffuse. Hole states near the top of the valence band form an energetic near continuum with the bulk and localize to the nonbonding sp3 orbitals on surface sulfur atoms. After localization, the holes form nonadiabatic small polarons that move between the sulfur orbitals on the surface of the particle in a series of uncorrelated, incoherent, thermally activated hops at room temperature. The surface-trapped holes are deeply in the weak-electronic coupling limit and, as a result, undergo slow diffusion.

The Dynamics of Water in Porous Two-Dimensional Crystals.

Porous two-dimensional crystals offer many promises for water desalination applications. For computer simulation to play a predictive role in this area, however, one needs to have reliable methods for simulating an atomistic system with hydrodynamic currents and interpretative tools to relate microscopic interactions to emergent macroscopic dynamical quantities, such as friction, slip length, and permeability. In this article, we use Gaussian dynamics, a nonequilibrium molecular dynamics method that provides microscopic insights into the interactions that control the flows of both simple liquids and liquid water through atomically small channels. In simulations of aqueous transport, we mimic the effect of changing the membrane chemical composition by adjusting the attractive strength of the van der Waals interactions between the membrane atoms and water. We find that the wetting contact angle, a common measure of a membrane's hydrophobicity, does not predict the permeability of a membrane. Instead, the hydrophobic effect is subtle, with both static and dynamic effects that can both help and hinder water transport through these materials. The competition between the static and dynamical hydrophobicity balances an atomic membrane's tendency to wet against hydrodynamic friction, and determines an optimal contact angle for water passage through nonpolar membranes. To a reasonable approximation, the optimal contact angle depends only on the aspect ratio of the pore. We also find that water molecules pass through the most hydrophobic membranes in a punctuated series of bursts that are separated by long pauses. A continuous-time Markov model of these data provides evidence of a molecular analogue to the clogging transition, a phenomenon observed in driven granular flows.

Atomistic Hydrodynamics and the Dynamical Hydrophobic Effect in Porous Graphene.

Mirroring their role in electrical and optical physics, two-dimensional crystals are emerging as novel platforms for fluid separations and water desalination, which are hydrodynamic processes that occur in nanoscale environments. For numerical simulation to play a predictive and descriptive role, one must have theoretically sound methods that span orders of magnitude in physical scales, from the atomistic motions of particles inside the channels to the large-scale hydrodynamic gradients that drive transport. Here, we use constraint dynamics to derive a nonequilibrium molecular dynamics method for simulating steady-state mass flow of a fluid moving through the nanoscopic spaces of a porous solid. After validating our method on a model system, we use it to study the hydrophobic effect of water moving through pores of electrically doped single-layer graphene. The trend in permeability that we calculate does not follow the hydrophobicity of the membrane but is instead governed by a crossover between two competing molecular transport mechanisms.

Tetracene Aggregation on Polar and Nonpolar Surfaces: Implications for Singlet Fission.

In molecular crystals that exhibit singlet fission, quantum yields depend strongly on intermolecular configurations that control the relevant electronic couplings. Here, we explore how noncovalent interactions between molecules and surfaces stabilize intermolecular structures with strong singlet fission couplings. Using molecular dynamics simulations, we studied the aggregation patterns of tetracene molecules on a solid surface as a function of surface polarity. Even at low surface concentrations, tetracene self-assembled into nanocrystallites where about 10-20% of the clustered molecules were part of at least one herringbone structure. The herringbone structure is the native structure of crystalline tetracene, which exhibits a high singlet fission quantum yield. Increasing the polarity of the surface reduced both the amount of clustering and the relative number of herringbone configurations, but only when the dipoles on the surface were orientationally disordered. These results have implications for the application of singlet fission in dye-sensitized solar cells.