Obtaining extended insight into molecular systems by probing multiple pathways in second-order nonlinear spectroscopy.

Second-order nonlinear spectroscopy is becoming an increasingly important technique in the study of interfacial systems owing to its marked ability to study molecular structures and interactions. The properties of such a system under investigation are contained within their intrinsic second-order susceptibilities which are mapped onto the measured nonlinear signals (e.g. sum-frequency generation) through the applied experimental settings. Despite this yielding a plethora of information, many crucial aspects of molecular systems typically remain elusive, for example the depth distributions, molecular orientation and local dielectric properties of its constituent chromophores. Here, it is shown that this information is contained within the phase of the measured signal and, critically, can be extracted through measurement of multiple nonlinear pathways (both the sum-frequency and difference-frequency output signals). Furthermore, it is shown that this novel information can directly be correlated to the characteristic vibrational spectra, enabling a new type of advanced sample characterization and a profound analysis of interfacial molecular structures. The theory underlying the different contributions to the measured phase of distinct nonlinear pathways is derived, after which the presented phase disentanglement methodology is experimentally demonstrated for model systems of self-assembled monolayers on several metallic substrates. The obtained phases of the local fields are compared to the corresponding phases of the nonlinear Fresnel factors calculated through the commonly used theoretical model, the three-layer model. It is found that, despite its rather crude assumptions, the model yields remarkable similarity to the experimentally obtained values, thus providing validation of the model for many sample classes.

Optical rectification and electro-optic sampling in quartz.

We report the electro-optic sampling (EOS) response and the terahertz (THz) optical rectification (OR) of the z-cut α-quartz. Due to its small effective second-order nonlinearity, large transparency window and hardness, freestanding thin quartz plates can faithfully measure the waveform of intense THz pulses with MV/cm electric-field strength. We show that both its OR and EOS responses are broad with extension up to ∼8 THz. Strikingly, the latter responses are independent of the crystal thickness, a plausible indication of dominant surface contribution to the total second-order nonlinear susceptibility of quartz at THz frequencies. Our study introduces the crystalline quartz as a reliable THz electro-optic medium for high field THz detection, and characterize its emission as a common substrate.

Near IR Bandgap Semiconducting 2D Conjugated Metal-Organic Framework with Rhombic Lattice and High Mobility.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) are emerging as a unique class of electronic materials. However, 2D c-MOFs with band gaps in the Vis-NIR and high charge carrier mobility are rare. Most of the reported conducting 2D c-MOFs are metallic (i.e. gapless), which largely limits their use in logic devices. Herein, we design a phenanthrotriphenylene-based, D2h -symmetric π-extended ligand (OHPTP), and synthesize the first rhombic 2D c-MOF single crystals (Cu2 (OHPTP)). The continuous rotation electron diffraction (cRED) analysis unveils the orthorhombic crystal structure at the atomic level with a unique slipped AA stacking. The Cu2 (OHPTP) is a p-type semiconductor with an indirect band gap of ≈0.50 eV and exhibits high electrical conductivity of 0.10 S cm-1 and high charge carrier mobility of ≈10.0 cm2  V-1 s-1 . Theoretical calculations underline the predominant role of the out-of-plane charge transport in this semiquinone-based 2D c-MOF.

Time-resolved terahertz-Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water.

The solvation of ions changes the physical, chemical and thermodynamic properties of water, and the microscopic origin of this behaviour is believed to be ion-induced perturbation of water's hydrogen-bonding network. Here we provide microscopic insights into this process by monitoring the dissipation of energy in salt solutions using time-resolved terahertz-Raman spectroscopy. We resonantly drive the low-frequency rotational dynamics of water molecules using intense terahertz pulses and probe the Raman response of their intermolecular translational motions. We find that the intermolecular rotational-to-translational energy transfer is enhanced by highly charged cations and is drastically reduced by highly charged anions, scaling with the ion surface charge density and ion concentration. Our molecular dynamics simulations reveal that the water-water hydrogen-bond strength between the first and second solvation shells of cations increases, while it decreases around anions. The opposite effects of cations and anions on the intermolecular interactions of water resemble the effects of ions on the stabilization and denaturation of proteins.

Rotational coherence of encapsulated ortho and para water in fullerene-C60 revealed by time-domain terahertz spectroscopy.

We resolve the real-time coherent rotational motion of isolated water molecules encapsulated in fullerene-C60 cages by time-domain terahertz (THz) spectroscopy. We employ single-cycle THz pulses to excite the low-frequency rotational motion of water and measure the subsequent coherent emission of electromagnetic waves by water molecules. At temperatures below ~ 100 K, C60 lattice vibrational damping is mitigated and the quantum dynamics of confined water are resolved with a markedly long rotational coherence, extended beyond 10 ps. The observed rotational transitions agree well with low-frequency rotational dynamics of single water molecules in the gas phase. However, some additional spectral features with their major contribution at ~2.26 THz are also observed which may indicate interaction between water rotation and the C60 lattice phonons. We also resolve the real-time change of the emission pattern of water after a sudden cooling to 4 K, signifying the conversion of ortho-water to para-water over the course of 10s hours. The observed long coherent rotational dynamics of isolated water molecules confined in C60 makes this system an attractive candidate for future quantum technology.

Energy transfer within the hydrogen bonding network of water following resonant terahertz excitation.

Energy dissipation in water is very fast and more efficient than in many other liquids. This behavior is commonly attributed to the intermolecular interactions associated with hydrogen bonding. Here, we investigate the dynamic energy flow in the hydrogen bond network of liquid water by a pump-probe experiment. We resonantly excite intermolecular degrees of freedom with ultrashort single-cycle terahertz pulses and monitor its Raman response. By using ultrathin sample cell windows, a background-free bipolar signal whose tail relaxes monoexponentially is obtained. The relaxation is attributed to the molecular translational motions, using complementary experiments, force field, and ab initio molecular dynamics simulations. They reveal an initial coupling of the terahertz electric field to the molecular rotational degrees of freedom whose energy is rapidly transferred, within the excitation pulse duration, to the restricted translational motion of neighboring molecules. This rapid energy transfer may be rationalized by the strong anharmonicity of the intermolecular interactions.

Macroscopic conductivity of aqueous electrolyte solutions scales with ultrafast microscopic ion motions.

Despite the widespread use of aqueous electrolytes as conductors, the molecular mechanism of ionic conductivity at moderate to high electrolyte concentrations remains largely unresolved. Using a combination of dielectric spectroscopy and molecular dynamics simulations, we show that the absorption of electrolytes at ~0.3 THz sensitively reports on the local environment of ions. The magnitude of these high-frequency ionic motions scales linearly with conductivity for a wide range of ions and concentrations. This scaling is rationalized within a harmonic oscillator model based on the potential of mean force extracted from simulations. Our results thus suggest that long-ranged ionic transport is intimately related to the local energy landscape and to the friction for short-ranged ion dynamics: a high macroscopic electrolyte conductivity is thereby shown to be related to large-amplitude motions at a molecular scale.

Terahertz-Magnetic-Field Induced Ultrafast Faraday Rotation of Molecular Liquids.

Rotation of the plane of the polarization of light in the presence of a magnetic field, known as the Faraday rotation, is a consequence of the electromagnetic nature of light and has been utilized in many optical devices. Current efforts aim to realize the ultrafast Faraday rotation on a subpicosecond timescale. Thereby, the Faraday medium should allow an ultrafast process by which in the presence of an ultrashort intense magnetic field, the light polarization rotates. We meet these criteria by applying an intense single cycle THz magnetic field to simple molecular liquids and demonstrate the rotation of the plane of polarization of an optical pulse traversing the liquids on a subpicosecond timescale. The effect is attributed to the deflection of an optically induced instantaneous electric polarization under the influence the THz magnetic field. The resolved Faraday rotation scales linearly with the THz magnetic field and quadratically with the molecular polarizability.

Specific Ion Effects on an Oligopeptide: Bidentate Binding Matters for the Guanidinium Cation.

Ion-protein interactions are important for protein function, yet challenging to rationalize owing to the multitude of possible ion-protein interactions. To explore specific ion effects on protein binding sites, we investigate the interaction of different salts with the zwitterionic peptide triglycine in solution. Dielectric spectroscopy shows that salts affect the peptide's reorientational dynamics, with a more pronounced effect for denaturing cations (Li+ , guanidinium (Gdm+ )) and anions (I- , SCN- ) than for weakly denaturing ones (K+ , Cl- ). The effects of Gdm+ and Li+ were found to be comparable. Molecular dynamics simulations confirm the enhanced binding of Gdm+ and Li+ to triglycine, yet with a different binding geometry: While Li+ predominantly binds to the C-terminal carboxylate group, bidentate binding to the terminus and the nearest amide is particularly important for Gdm+ . This bidentate binding markedly affects peptide conformation, and may help to explain the high denaturation activity of Gdm+ salts.

Dissecting Hofmeister Effects: Direct Anion-Amide Interactions Are Weaker than Cation-Amide Binding.

Whereas there is increasing evidence for ion-induced protein destabilization through direct ion-protein interactions, the strength of the binding of anions to proteins relative to cation-protein binding has remained elusive. In this work, the rotational mobility of a model amide in aqueous solution was used as a reporter for the interactions of different anions with the amide group. Protein-stabilizing salts such as KCl and KNO3 do not affect the rotational mobility of the amide. Conversely, protein denaturants such as KSCN and KI markedly reduce the orientational freedom of the amide group. Thus these results provide evidence for a direct denaturation mechanism through ion-protein interactions. Comparing the present findings with results for cations shows that in contrast to common belief, anion-amide binding is weaker than cation-amide binding.