Two-dimensional topological insulators (2D TIs) are a remarkable class of atomically thin layered materials that exhibit unique symmetry-protected helical metallic edge states with an insulating interior. Recent years have seen a tremendous surge in research of this intriguing new state of quantum matter. In this Perspective, we summarize major milestones and the most significant progress in the latest developments of material discovery and property characterization in 2D TI research. We categorize the large number and rich variety of theoretically proposed 2D TIs based on the distinct mechanisms of topological phase transitions, and we systematically analyze and compare their structural, chemical, and physical characteristics. We assess the current status and challenges of experimental synthesis and potential device applications of 2D TIs and discuss prospects of exciting new opportunities for future research and development of this fascinating class of materials.

Influences of solvent molecules on S_N2 reaction dynamics of microsolvated F^–(H₂O)_n with CH₃I, for n = 0–3, are uncovered by direct chemical dynamics simulations. The direct substitution mechanism, which is important without microsolvation, is quenched dramatically upon increasing hydration. The water molecules tend to force reactive encounters to proceed through the prereaction collision complex leading to indirect reaction. In contrast to F^–(H₂O), reaction with higher hydrated ions shows a strong propensity for ion desolvation in the entrance channel, diminishing steric hindrance for nucleophilic attack. Thus, nucleophilic substitution avoids the potential energy barrier with all of the solvent molecules intact and instead occurs through the less solvated barrier, which is energetically unexpected because the former barrier has a lower energy. The work presented here reveals a trade-off between reaction energetics and steric effects, with the latter found to be crucial in understanding how hydration influences microsolvated S_N2 dynamics.

We present a new solution for classical polarization that does not require any self-consistent field iterations, the aspect of classical polarization that makes it computationally expensive. The new method builds upon our iEL/SCF Lagrangian scheme that defines a set of auxiliary induced dipoles whose original purpose was to serve as a time-reversible initial guess to the SCF solution of the set of real induced dipoles. In the new iEL/0-SCF approach the auxiliary dipoles now drive the time evolution of the real induced dipoles such that they stay close to the Born–Oppenheimer surface in order to achieve a truly SCF-less method. We show that the iEL/0-SCF exhibits no loss of simulation accuracy when analyzed across bulk water, low to high concentration salt solutions, and small solutes to large proteins in water. In addition, iEL/0-SCF offers significant computational savings over more expensive SCF calculations based on traditional 1 fs time step integration using symplectic integrators and is as fast as reversible reference system propagator algorithms with an outer 2 fs time step.

For the first time, ultrafast deactivations of photoexcited water-solvated pyrimidine nucleosides are mapped employing hybrid QM(CASPT2)/MM(AMBER) optimizations that account for explicit solvation, sugar effects, and dynamically correlated potential energy surfaces. Low-energy S₁/S₀ ring-puckering and ring-opening conical intersections (CIs) are suggested to drive the ballistic coherent subpicosecond (<200 fs) decays observed in each pyrimidine, the energetics controlling this processes correlating with the lifetimes observed. A second bright ¹π₂π* state, promoting excited-state population branching and leading toward a third CI with the ground state, is proposed to be involved in the slower ultrafast decay component observed in Thd/Cyd. The transient spectroscopic signals of the competitive deactivation channels are computed for the first time. A general unified scheme for ultrafast deactivations, spanning the sub- to few-picosecond time domain, is eventually delivered, with computed data that matches the experiments and elucidates the intrinsic photoprotection mechanism in solvated pyrimidine nucleosides.

We propose a systematic approach to the basis set extension for nonadiabatic dynamics of entangled combination of nuclear coherent states (CSs) evolving according to the time-dependent variational principle (TDVP). The TDVP provides a rigorous framework for fully quantum nonadiabatic dynamics of closed systems; however, the quality of results strongly depends on available basis functions. Starting with a single nuclear CS replicated vertically on all electronic states, our approach clones this function when replicas of the CS on different electronic states experience increasingly different forces. Created clones move away from each other (decohere), extending the basis set. To determine a moment for cloning, we introduce generalized forces based on derivatives that maximally contribute to a variation of the total quantum action and thus account for entanglement of all basis functions.

Aqueous nanocrystalline suspensions provide a simple and efficient medium for performing transmission spectroscopy measurements in the solid state. In this Letter we describe the use of laser flash photolysis methods to analyze the photochemistry of 2-azidobiphenyl and several aryl-substituted derivatives. We show that all the crystalline compounds analyzed in this study transform quantitatively into carbazole products via a crystal-to-crystal reconstructive phase transition. While the initial steps of the reaction cannot be followed within the time resolution of our instrument (ca. 8 ns), we detected the primary isocarbazole photoproducts and analyzed the kinetics of their formal 1,5-H shift reactions, which take place in time scales that range from a few nanoseconds to several microseconds. It is worth noting that the high reaction selectivity observed in the crystalline state translates into a clean and simple kinetic process compared to that in solution.

Solid-state luminescent materials with long lifetimes are the subject of ever-growing interest from both a scientific and a technological point of view. However, when dealing with organic compounds, the achievement of highly efficient materials is limited by aggregation-caused quenching (ACQ) phenomena on one side and by ultrafast deactivation of the excited states on the other. Here, we report on a simple organic molecule, namely, cyclic triimidazole (C₉H₆N₆), 1, showing crystallization-induced emissive (CIE) behavior and, in particular, ultralong phosphorescence due to strong coupling in H-aggregated molecules. Our experimental data reveal that luminescence lifetimes up to 1 s, which are several orders of magnitude longer than those of conventional organic fluorophores, can be realized under ambient conditions, thus expanding the class of organic materials for phosphorescence applications.

Impulsive Raman excitation in neat organic liquids far from resonance is followed using chirped broad-band supercontinuum probe pulses. Spectral modulations due to impulsively induced coherent vibrations vary in intensity 10-fold as a function of the probe’s linear chirp. Simulations clarify why the vibrational signature is maximized for a group delay dispersion (GDD) in reduced units of ν_vib^–2 = 0.5 while a probe GDD of twice that quenches the same spectral modulations. Accordingly, recent claims that chirped white-light probe pulses provide equivalent information on material response to their compressed analogues must be taken with caution. In particular, interactions that induce spectral shifts in the probe depend crucially on the arrival chronology of the continuum colors. On one hand, this presents limitations to application of chirped continuum radiation as-is in pump–probe experiments. It also presents the opportunity for using this dependence to control the relative amplitude of nonresonant interactions in pump–probe signals such as that of solvent vibrations.

Hydrophobins are surface-active proteins that form a hydrophobic, water-repelling film around aerial fungal structures. They have a compact, particle-like structure, in which hydrophilic and hydrophobic regions are spatially separated. This surface property renders them amphiphilic and is reminiscent of synthetic Janus particles. Here we report surface-specific chiral and nonchiral vibrational sum-frequency generation spectroscopy (VSFG) measurements of hydrophobins adsorbed to their natural place of action, the air–water interface. We observe that hydrophobin molecules undergo a reversible change in orientation (tilt) at the interface when the pH is varied. We explain this local orientation toggle from the modification of the interprotein interactions and the interaction of hydrophobin with the water solvent, following the pH-induced change of the charge state of particular amino acids.

Selectively labeled GroEL protein was produced in living deuterated bacterial cells to enhance its neutron scattering signal above that of the intracellular milieu. Quasi-elastic neutron scattering shows that the in-cell diffusion coefficient of GroEL was (4.7 ± 0.3) × 10^–12 m²/s, a factor of 4 slower than its diffusion coefficient in buffer solution. Internal protein dynamics showed a relaxation time of (65 ± 6) ps, a factor of 2 slower compared to the protein in solution. Comparison to the literature suggests that the effective diffusivity of proteins depends on the length and time scale being probed. Retardation of in-cell diffusion compared to the buffer becomes more significant with the increasing probe length scale, suggesting that intracellular diffusion of biomolecules is nonuniform over the cellular volume. The approach outlined here enables investigation of protein dynamics within living cells to open up new lines of research using “in-cell neutron scattering” to study the dynamics of complex biomolecular systems.

Amphiphile self-assembly is an essential bottom-up approach of fabricating advanced functional materials. Self-assembled materials with desired structures are often obtained through thermodynamic control. Here, we demonstrate that the selection of kinetic pathways can lead to drastically different self-assembled structures, underlining the significance of kinetic control in self-assembly. By constructing kinetic network models from large-scale molecular dynamics simulations, we show that two largely similar amphiphiles, 1-[11-oxo-11-(pyren-1-ylmethoxy)-undecyl]pyridinium bromide (PYR) and 1-(11-((5a1,8a-dihydropyren-1-yl)methylamino)-11-oxoundecyl)pyridinium bromide (PYN), prefer distinct kinetic assembly pathways. While PYR prefers an incremental growth mechanism and forms a nanotube, PYN favors a hopping growth pathway leading to a vesicle. Such preference was found to originate from the subtle difference in the distributions of hydrophobic and hydrophilic groups in their chemical structures, which leads to different rates of the adhesion process among the aggregating micelles. Our results are in good agreement with experimental results, and accentuate the role of kinetics in the rational design of amphiphile self-assembly.

Over the past several decades, tremendous efforts have been made to understand the fundamental physics of block copolymer (BCP) self-assembly in bulk or thin films, and this has led to the development of BCP-based bottom-up nanofabrication. BCPs also form periodic nanostructures at the air/water interface, which has potential application to ultrathin-film nanopatterning with molecular-level precision. Nonetheless, controlling the nanostructure formation at the air/water interface is restricted by the inherent parameters of BCPs; BCP morphology is determined by the hydrophilic-to-hydrophobic block ratio. Here we show that controlling the spreading area of BCPs at the air/water interface can tune the shape and size of BCP structures, suggesting a new phase diagram of BCP structures as a function of the relative block fraction and spreading area. A neat polystyrene-b-poly(2-vinylpyridine), known to form a dot morphology, instead forms a strand or planar morphology when the spreading area is varied with Langmuir–Blodgett technique.

Nanostructured metals subject to local optical interrogation can generate open-circuit photovoltages potentially useful for energy conversion and photodetection. We report a study of the photovoltage as a function of illumination position in single-metal Au nanowires and nanowires with nanogaps formed by electromigration. We use a laser scanning microscope to locally heat the metal nanostructures via excitation of a local plasmon resonance and direct absorption. In nanowires without nanogaps, where charge transport is diffusive, we observe voltage distributions consistent with thermoelectricity, with the local Seebeck coefficient depending on the width of the nanowire. In the nanowires with nanogaps, where charge transport is by tunneling, we observe large photovoltages up to tens of mV, with magnitude, polarization dependence, and spatial localization that follow the plasmon resonance in the nanogap. This is consistent with a model of photocurrent across the nanogap carried by the nonequilibrium, “hot” carriers generated upon plasmon excitation.

The optoelectronic properties of amorphous conjugated polymers are sensitive to the details of the conformational disorder, and spectroscopy provides the means for structural characterization of the fragments of the chain that interact with light—“chromophores”. A faithful interpretation of spectroscopic conformational signatures, however, presents a theoretical challenge. Here we investigate the relationship between the ground-state optical gaps, the properties of the excited states, and the structural features of chromophores of a single molecule poly(3-hexyl)-thiophene (P3HT) using quantum–classical atomistic simulations. Our results demonstrate that chromophoric disorder arises through the interplay between excited-state delocalization and electron–hole polarization, controlled by the torsional disorder introduced by side chains. Within this conceptual framework, we predict and explain the counterintuitive spectral behavior of P3HT, a red-shifted absorption, despite shortening of chromophores, with increasing temperature. This discussion introduces the concept of disorder-induced separation of charges in amorphous conjugated polymers.

The use of hybrid organic–inorganic perovskites in optoelectronic applications are attracting an interest because of their outstanding characteristics, which enable a remarkable enhancement of device efficiency. However, solution-processed perovskite crystals unavoidably contain defect sites that cause hysteresis in perovskite solar cells (PeSCs) and blinking in perovskite light-emitting diodes (PeLEDs). Here, we report significant beneficial effects using a new treatment based on amine-based passivating materials (APMs) to passivate the defect sites of methylammonium lead tribromide (MAPbBr₃) through coordinate bonding between the nitrogen atoms and undercoordinated lead ions. This treatment greatly enhanced the PeLED’s efficiency, with an external quantum efficiency (EQE) of 6.2%, enhanced photoluminescence (PL), a lower threshold for amplified spontaneous emission (ASE), a longer PL lifetime, and enhanced device stability. Using confocal microscopy, we observed the cessation of PL blinking in perovskite films treated with ethylenediamine (EDA) due to passivation of the defect sites in the MAPbBr₃.

Lead halide perovskite solar cells have recently emerged as a very promising photovoltaic technology due to their excellent power conversion efficiencies; however, the toxicity of lead and the poor stability of perovskite materials remain two main challenges that need to be addressed. Here, for the first time, we report a lead-free, highly stable C₆H₄NH₂CuBr₂I compound. The C₆H₄NH₂CuBr₂I films exhibit extraordinary hydrophobic behavior with a contact angle of ∼90°, and their X-ray diffraction patterns remain unchanged even after 4 h of water immersion. UV/vis absorption spectrum shows that C₆H₄NH₂CuBr₂I compound has an excellent optical absorption over the entire visible spectrum. We applied this copper-based light absorber in printable mesoscopic solar cell for the initial trial and achieved a power conversion efficiency of ∼0.5%. Our study represents an alternative pathway to develop low-toxic and highly stable organic–inorganic hybrid materials for photovoltaic application.

Solution-processable organometal halide perovskites have been emerging as very promising materials for light-emitting diodes (LEDs) because of their high color purity, low cost, and high photoluminescence quantum yield. However, their electroluminescent performance is still limited by incomplete surface coverage and inefficient charge injection into the perovskite. Here, we demonstrate highly efficient perovskite LEDs (PeLEDs) incorporating full film coverage and bipolar charge injection within the active layer by introducing perovskite precursor poly(9-vinylcarbazole):1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (PVK:TPBi) toluene solution into CH₃NH₃PbBr₃ N,N-dimethylformamide solution. Both the film coverage and the charge injections were simultaneously improved by antisolvent of toluene and PVK:TPBi matrix, respectively. After the film morphology and weight ratio of PVK:TPBi were carefully adjusted, the optimal PeLEDs gave efficient emission with turn-on voltage of ∼2.8 V, maximum luminance of ∼7263 cd/m², maximum current efficiency of ∼9.45 cd/A, and maximum external quantum efficiency of ∼2.28%, which are among the best results based on MAPbBr₃ reported to date.

Indoor utilization of emerging photovoltaics is promising; however, efficiency characterization under room lighting is challenging. We report the first round-robin interlaboratory study of performance measurement for dye-sensitized photovoltaics (cells and mini-modules) and one silicon solar cell under a fluorescent dim light. Among 15 research groups, the relative deviation in power conversion efficiency (PCE) of the samples reaches an unprecedented 152%. On the basis of the comprehensive results, the gap between photometry and radiometry measurements and the response of devices to the dim illumination are identified as critical obstacles to the correct PCE. Therefore, we use an illuminometer as a prime standard with a spectroradiometer to quantify the intensity of indoor lighting and adopt the reverse-biased current–voltage (I–V) characteristics as an indicator to qualify the I–V sampling time for dye-sensitized photovoltaics. The recommendations can brighten the prospects of emerging photovoltaics for indoor applications.

We have accurately determined the exciton binding energy and reduced mass of single crystals of methylammonium lead triiodide using magneto-reflectivity at very high magnetic fields. The single crystal has excellent optical properties with a narrow line width of ∼3 meV for the excitonic transitions and a 2s transition that is clearly visible even at zero magnetic field. The exciton binding energy of 16 ± 2 meV in the low-temperature orthorhombic phase is almost identical to the value found in polycrystalline samples, crucially ruling out any possibility that the exciton binding energy depends on the grain size. In the room-temperature tetragonal phase, an upper limit for the exciton binding energy of 12 ± 4 meV is estimated from the evolution of 1s–2s splitting at high magnetic field.

A facile synthetic method for doped conjugated molecules by a heating process is demonstrated. Br-terminated terthiophene precursors are encapsulated in single-walled carbon nanotubes by a vapor-phase reaction, and additional heat treatment promotes the thermal condensation of the precursors. Transmission electron microscopy observations and optical measurements show the successful synthesis of sexithiophenes and their doping (oxidation) by Br dopants generated by the condensation reaction. This study provides a new strategy for the synthesis of the doped conjugated polymers from single-species molecules by only a heating process.

The enchanting Dirac fermions in graphene stimulated us to seek other 2D Dirac materials, and boron monolayers may be a good candidate. So far, a number of monolayer boron sheets have been theoretically predicted, and three have been experimentally prepared. However, none of intrinsic sheets possess Dirac electrons near the Fermi level. Herein, by means of density functional theory computations, we identified a new boron monolayer, namely, hr-sB, with two types of Dirac fermions coexisting in the sheet: One type is related to Dirac nodal lines traversing Brillouin zone (BZ) with velocities approaching 10⁶ m/s, and the other is related to tilted semi-Dirac cones with strong anisotropy. This newly predicted boron monolayer consists of hexagon and rhombus stripes. With an exceptional stability comparable to the experimentally achieved boron sheets, it is rather optimistic to grow hr-sB on some suitable substrates such as the Ag (111) surface.

Organolead halide perovskites MAPbX₃ (MA = CH₃NH₃⁺, X = Cl^–, Br^–, or I^–) are known to undergo reversible halide exchange reactions, enabling bandgap tuning over the visible light region. Using single-particle photoluminescence (PL) imaging for in situ observation, we have studied the structure-dependent charge dynamics during halide exchange with iodide ions on an MAPbBr₃ crystal. In particular, we optically detected nanometer-scale iodide-rich domains (i.e., MAPbBrI₂) and found that their lifetimes of several tens of milliseconds are limited by reaction with diffusing vacancies. Furthermore, it was discovered that these domains effectively collect the charge carriers from the bulk crystal, thus resulting in amplified spontaneous emission (ASE) under continuous-wave laser irradiation. Our findings will provide direction for development of perovskite heterostructures with enhanced charge utilization.

The high-concentration stable dispersion of free-standing mono- or few-layer transition metal dichalcogenide (TMD) nanosheets (NSs) remains a significant barrier for their application in solution-processed optoelectronic devices. Here, we report oleylamine (OLA)- and dodecanethiol (DDT)-assisted exfoliation of MoS₂ NSs in nonpolar organic solvent 1,2-dichlorobenzene (DCB), which enables high-concentration stable dispersion of free-standing mono- or few-layer NSs. The functionalized MoS₂ NSs were further utilized for the fabrication of solution-processed 0D–2D hybrids of CuInS₂ quantum dots (CIS QDs) and MoS₂ NSs. The strong photoluminescence (PL) quenching and decreased PL lifetimes of CIS QDs attached to MoS₂ NSs indicates efficient charge transfer from photoexcited CIS to MoS₂ NSs. The photocurrent of CIS/MoS₂ hybrid devices is dramatically enhanced compared to that of pure CIS and pristine MoS₂-based devices, confirming that efficient charge separation and transfer occur from CIS QDs to MoS₂ NSs.

Organic–inorganic hybrid perovskite has appeared as one of the leading materials for realizing solution-based high-performing optoelectronic devices. The charge transport properties in this class of material are quite intriguing and still need to be carefully investigated. The temperature-dependent electrical property of methylammonium lead iodide (CH₃NH₃PbI₃) has been investigated by employing positron annihilation spectroscopy (PAS), which unambiguously reveals the gradual formation of open volume defects with the enhancement in temperature. The high-temperature ionic conductivity is due to the generation of both cationic (CH₃NH₃⁺) and anionic (I^–) vacancies, possibly because of the elimination of methylammonium iodide (CH₃NH₃I) as identified from the coincidence Doppler broadening (CDB) of the positron annihilation spectroscopy. Further, the evolution of temperature-dependent defect density and corresponding electrical responses has been correlated with the structural phase transitions of CH₃NH₃PbI₃. This is the first ever report of temperature-dependent PAS measurement on hybrid lead halide perovskites to understand the nature and the origin of its electrical characteristics arising due to the variation in temperature.

We investigate the formation mechanisms of vacancy-ordered phase and collective mass transport in epitaxial SrCrO_3−δ films using ab initio simulations within the density functional theory formalism. We show that as the concentration of oxygen vacancies (V_O) increases, they form 1D chains that feature Cr-centered tetrahedra. Aggregation of these 1D V_O chains results in the formation of (111)-oriented oxygen-deficient planes and an extended vacancy-ordered phase observed in recent experiments. We discuss atomic-scale mechanisms enabling the quasi-2D V_O aggregates to expand along and translate across (111) planes. The corresponding lowest activation energy pathways necessarily involve rotation of Cr-centered tetrahedra, which emerges as a universal feature of fast ionic conduction in complex oxides. These findings explain reversible oxidation and reduction in SrCrO_3−δ at low temperatures and provide insights into transient behavior necessary to harness ionic conductive oxides for high-performance and low-temperature electrochemical reactors.

In contrast with theoretical predictions in which anatase TiO₂(001) and its (1 × 4) reconstructed surfaces are highly reactive, recent experimental results show this surface to be inert except for the defect sites. In this report, based on a systematic study of anatase TiO₂(001)-(1 × 4) surface using first-principles calculations, the tensile stress is shown to play a crucial role on the surface reactivity. The predicted high reactivity based on add-molecule model is due to the large surface tensile stress, which can be easily suppressed by a stress-release mechanism. We show that various surface defects can induce stress release concomitantly with surface passivation. Thus the synthesis of anatase(001) surface with few defects is essential to improve the reactivity, which can be achieved, for example, via H₂O adsorption. Our study provides a uniform interpretation of controversial experimental observations and theoretical predictions on anatase TiO₂(001) surface and further proposes new insights into the origin of surface reactivity.

Herein, we utilize surface-enhanced hyper-Raman scattering (SEHRS) under resonance conditions to probe the adsorbate geometry of rhodamine 6G (R6G) on silver colloids. Our results show resonance SEHRS is highly sensitive to molecular orientation due to non-Condon effects, which do not appear in its linear counterpart surface-enhanced Raman scattering. Comparisons between simulated and measured SEHRS spectra reveal R6G adsorbs mostly perpendicular to the nanoparticle surface along the ethylamine groups with the xanthene ring oriented edgewise. Our results expand upon previous studies that rely on indirect, qualitative probes of R6G’s orientation on plasmonic substrates. More importantly, this work represents the first determination of adsorbate geometry by SEHRS and opens up the possibility to study the orientation of single molecules in complex, plasmonic environments.

A fundamental understanding of the rich electronic structures of electronically doped semiconductor nanocrystals is vital for assessing the utility of these materials for future applications from solar cells to redox catalysis. Here, we examine the use of magnetic circular dichroism (MCD) spectroscopy to probe the infrared localized surface plasmon resonances of p-Cu_2–xSe, n-ZnO, and tin-doped In₂O₃ (n-ITO) nanocrystals. We demonstrate that the MCD spectra of these nanocrystals can be analyzed by invoking classical cyclotron motions of their excess charge carriers, with experimental MCD signs conveying the carrier types (n or p) and experimental MCD intensities conveying the cyclotron splitting magnitudes. The experimental cyclotron splittings can then be used to quantify carrier effective masses (m*), with results that agree with bulk in most cases. MCD spectroscopy thus offers a unique measure of m* in free-standing colloidal semiconductor nanocrystals, raising new opportunities to investigate the influence of various other synthetic or environmental parameters on this fundamentally important electronic property.

Switching the magnetic properties of organic semiconductors on a metal surface has thus far largely been limited to molecule-by-molecule tip-induced transformations in scanned probe experiments. Here we demonstrate with molecular resolution that collective control of activated Kondo screening can be achieved in thin-films of the organic semiconductor titanyl phthalocyanine on Cu(110) to obtain tunable concentrations of Kondo impurities. Using low-temperature scanning tunneling microscopy and spectroscopy, we show that a thermally activated molecular distortion dramatically shifts surface–molecule coupling and enables ensemble-level control of Kondo screening in the interfacial spin system. This is accompanied by the formation of a temperature-dependent Abrikosov–Suhl–Kondo resonance in the local density of states of the activated molecules. This enables coverage-dependent control over activation to the Kondo screening state. Our study thus advances the versatility of molecular switching for Kondo physics and opens new avenues for scalable bottom-up tailoring of the electronic structure and magnetic texture of organic semiconductor interfaces at the nanoscale.

The enormous versatility in the properties of carbon materials depends on the content of the sp² and sp³ covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C₆H₆ and C₆D₆ up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures show the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C₆D₆ shed light on the mechanism of polymerization of benzene. We find that C₆D₆-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp³ hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C₆D₆ is observed.

Chiral nanomaterials are characterized by handedness morphology on the nanoscale, manifested as preferential interaction with circularly polarized light. However, the origin of this light–matter interaction remains elusive. Here we simulated a model of chiral helical arrays of plasmonic nanoparticles with central anisotropic nanopillars to examine the effect of birefringence on the collective chiroptical response. Contrary to typical assumptions in previous works, we varied the biaxial refractive indices of the central nanopillars and observed a significant modulation of optical activity by calculating and characterizing circular dichroism (CD) spectra. The chiroptical response exhibited a sign change compared with that of the isotropic condition in a specific parametric range of negative birefringence. In addition, the CD peak increased by 3 to 16 as the ordinary refractive index increased from 1.5 to 3.0. These results are likely to be useful for designing chiral nanomaterials for applications in metamaterials, biosensors, and optoelectrical devices.

A major hazard to jet engines posed by volcanic ash is linked to the wetting and spreading of molten ash droplets on engine component surfaces. Here, using the sessile drop method, we study the evolution of the wettability and spreading of volcanic ash. We employ rapid temperature changes up to 1040–1450 °C, to replicate the heating conditions experienced by volcanic ash entering an operating jet engine. In this scenario, samples densify as particles coalesce under surface tension until they form a large system-sized droplet (containing remnant gas bubbles and crystals), which subsequently spreads on the surface. The data exhibit a transition from a heterogeneous to a homogeneous wetting regime above 1315 °C as crystals in the drops are dissolved in the melt. We infer that both viscosity and microstructural evolution are key controls on the attainment of equilibrium in the wetting of molten volcanic ash droplets.