Fluids and Electrolytes under Confinement in Single-Digit Nanopores.

Confined fluids and electrolyte solutions in nanopores exhibit rich and surprising physics and chemistry that impact the mass transport and energy efficiency in many important natural systems and industrial applications. Existing theories often fail to predict the exotic effects observed in the narrowest of such pores, called single-digit nanopores (SDNs), which have diameters or conduit widths of less than 10 nm, and have only recently become accessible for experimental measurements. What SDNs reveal has been surprising, including a rapidly increasing number of examples such as extraordinarily fast water transport, distorted fluid-phase boundaries, strong ion-correlation and quantum effects, and dielectric anomalies that are not observed in larger pores. Exploiting these effects presents myriad opportunities in both basic and applied research that stand to impact a host of new technologies at the water-energy nexus, from new membranes for precise separations and water purification to new gas permeable materials for water electrolyzers and energy-storage devices. SDNs also present unique opportunities to achieve ultrasensitive and selective chemical sensing at the single-ion and single-molecule limit. In this review article, we summarize the progress on nanofluidics of SDNs, with a focus on the confinement effects that arise in these extremely narrow nanopores. The recent development of precision model systems, transformative experimental tools, and multiscale theories that have played enabling roles in advancing this frontier are reviewed. We also identify new knowledge gaps in our understanding of nanofluidic transport and provide an outlook for the future challenges and opportunities at this rapidly advancing frontier.

Phonon heat transfer across a vacuum through quantum fluctuations.

Heat transfer in solids is typically conducted through either electrons or atomic vibrations known as phonons. In a vacuum, heat has long been thought to be transferred by radiation but not by phonons because of the lack of a medium1. Recent theory, however, has predicted that quantum fluctuations of electromagnetic fields could induce phonon coupling across a vacuum and thereby facilitate heat transfer2-4. Revealing this unique quantum effect experimentally would bring fundamental insights to quantum thermodynamics5 and practical implications to thermal management in nanometre-scale technologies6. Here we experimentally demonstrate heat transfer induced by quantum fluctuations between two objects separated by a vacuum gap. We use nanomechanical systems to realize strong phonon coupling through vacuum fluctuations, and observe the exchange of thermal energy between individual phonon modes. The experimental observation agrees well with our theoretical calculations and is unambiguously distinguished from other effects such as near-field radiation and electrostatic interaction. Our discovery of phonon transport through quantum fluctuations represents a previously unknown mechanism of heat transfer in addition to the conventional conduction, convection and radiation. It paves the way for the exploitation of quantum vacuum in energy transport at the nanoscale.

Photoabsorption Imaging at Nanometer Scales Using Secondary Electron Analysis.

Optical imaging with nanometer resolution offers fundamental insights into light-matter interactions. Traditional optical techniques are diffraction limited with a spatial resolution >100 nm. Optical super-resolution and cathodoluminescence techniques have higher spatial resolutions, but these approaches require the sample to fluoresce, which many materials lack. Here, we introduce photoabsorption microscopy using electron analysis, which involves spectrally specific photoabsorption that is locally probed using a scanning electron microscope, whereby a photoabsorption-induced surface photovoltage modulates the secondary electron emission. We demonstrate spectrally specific photoabsorption imaging with sub-20 nm spatial resolution using silicon, germanium, and gold nanoparticles. Theoretical analysis and Monte Carlo simulations are used to explain the basic trends of the photoabsorption-induced secondary electron signal. Based on our current experiments and this analysis, we expect that the spatial resolution can be further improved to a few nanometers, thereby offering a general approach for nanometer-scale optical spectroscopic imaging and material characterization.

Imaging Arrangements of Discrete Ions at Liquid-Solid Interfaces.

The individual and collective behavior of ions near electrically charged interfaces is foundational to a variety of electrochemical phenomena encountered in biology, energy, and the environment. While many theories have been developed to predict the interfacial arrangements of counterions, direct experimental observations and validations have remained elusive. Utilizing cryo-electron microscopy, here we directly visualize individual counterions and reveal their discrete interfacial layering. Comparison with simulations suggests the strong effects of finite ionic size and electrostatic interactions. We also uncover correlated ionic structures under extreme confinement, with the channel widths approaching the ionic diameter (∼1 nm). Our work reveals the roles of ionic size, valency, and confinement in determining the structures of liquid-solid interfaces and opens up new opportunities to study such systems at the single-ion level.

Realization of Translational Symmetry in Trapped Cold Ion Rings.

We crystallize up to 15 ^{40}Ca^{+} ions in a ring with a microfabricated silicon surface Paul trap. Delocalization of the Doppler laser-cooled ions shows that the translational symmetry of the ion ring is preserved at millikelvin temperatures. By characterizing the collective motion of the ion crystals, we identify homogeneous electric fields as the dominant symmetry-breaking mechanism at this energy scale. With increasing ion numbers, such detrimental effects are reduced. We predict that, with only a ten-ion ring, uncompensated homogeneous fields will not break the translational symmetry of the rotational ground state. This experiment opens a door towards studying quantum many-body physics with translational symmetry at the single-particle level.

Unidirectional spectral singularities.

We propose a class of spectral singularities emerging from the coincidence of two independent singularities with highly directional responses. These spectral singularities result from resonance trapping induced by the interplay between parity-time symmetry and Fano resonances. At these singularities, while the system is reciprocal in terms of a finite transmission, a simultaneous infinite reflection from one side and zero reflection from the opposite side can be realized.

Imaging the electron charge density in monolayer MoS2 at the Ångstrom scale.

Four-dimensional scanning transmission electron microscopy (4D-STEM) has recently gained widespread attention for its ability to image atomic electric fields with sub-Ångstrom spatial resolution. These electric field maps represent the integrated effect of the nucleus, core electrons and valence electrons, and separating their contributions is non-trivial. In this paper, we utilized simultaneously acquired 4D-STEM center of mass (CoM) images and annular dark field (ADF) images to determine the projected electron charge density in monolayer MoS2. We evaluate the contributions of both the core electrons and the valence electrons to the derived electron charge density; however, due to blurring by the probe shape, the valence electron contribution forms a nearly featureless background while most of the spatial modulation comes from the core electrons. Our findings highlight the importance of probe shape in interpreting charge densities derived from 4D-STEM and the need for smaller electron probes.

Mitochondrial Phylogenomics Suggests Complex Evolutionary Pattern of Pronotal Foliaceous Mimicry in Hierodulinae (Mantodea: Mantidae), with Description of a New Species of Rhombodera Burmeister, 1838 from China.

Hierodulinae is a species-rich mantid subfamily, with some species bearing a notable leaf-like pronotum. However, the evolutionary pattern and taxonomic significance of the leaf-like pronotum are largely unknown. Here, we present a phylogenomic analysis of the Hierodulinae genera Rhombodera Burmeister, 1838, and Hierodula Burmeister, 1838 based on mitochondrial genomes. We also describe a new species, namely Rhombodera hyalina sp. nov. from Guangxi, China. Our phylogenetic result, together with the evidence from male genitalia, suggests the division of the Oriental Hierodula and Rhombodera complex into three clades. We find a complex pattern on the evolution of the leaf-like pronotum, which is present in at least five lineages, respectively, of the above three clades.