Resolving the Fundamentals of Magnetotransport in Metals with Ultrafast Terahertz Spectroscopy

2016

Using terahertz spectroscopy we directly resolved the fundamentals of spin-dependent conductivity in ferromagnetic metals. We quantified the differences in conduction by Fermi-level electrons with opposite spins on the sub-100 fs timescale of electron momentum scattering.

Experimental and theoretical evidence for bilayer-by-bilayer surface melting of crystalline ice

2017

On the surface of water ice, a quasi-liquid layer (QLL) has been extensively reported at temperatures below its bulk melting point at 273 K. Approaching the bulk melting temperature from below, the thickness of the QLL is known to increase. To elucidate the precise temperature variation of the QLL, and its nature, we investigate the surface melting of hexagonal ice by combining noncontact, surface-specific vibrational sum frequency generation (SFG) spectroscopy and spectra calculated from molecular dynamics simulations. Using SFG, we probe the outermost water layers of distinct single crystalline ice faces at different temperatures. For the basal face, a stepwise, sudden weakening of the hy…

Engineering von Proteinen an Oberflächen: Von komplementärer Charakterisierung zu Materialoberflächen mit maßgeschneiderten Funktionen

2018

IM30 triggers membrane fusion in cyanobacteria and chloroplasts

2015

The thylakoid membrane of chloroplasts and cyanobacteria is a unique internal membrane system harbouring the complexes of the photosynthetic electron transfer chain. Despite their apparent importance, little is known about the biogenesis and maintenance of thylakoid membranes. Although membrane fusion events are essential for the formation of thylakoid membranes, proteins involved in membrane fusion have yet to be identified in photosynthetic cells or organelles. Here we show that IM30, a conserved chloroplast and cyanobacterial protein of approximately 30 kDa binds as an oligomeric ring in a well-defined geometry specifically to membranes containing anionic lipids. Triggered by Mg2+, membr…

Probing giant magnetoresistance with THz spectroscopy

2014

We observe a giant magnetoresistance effect in CoFe/Cu-based multistack using THz time-domain spectroscopy. The magnetic field-dependent dc conductivity, electron scattering time, as well as spin-asymmetry parameter of the structure are successfully determined.

Large area conductive nanoaperture arrays with strong optical resonances and spectrally flat terahertz transmission

2017

Using simple and inexpensive nanosphere lithography, we produce large, centimeter-squared sized thin golden films patterned with a hexagonal array of nanoapertures with controllable dimensions on the order of 100–300 nm, spaced by a 350–375 nm pitch distance. The optical transmission spectra of our samples are dominated by the resonant plasmonic features in the spectral range 500–700 nm, caused by the nanostructure in the film. At the same time, the transmission at terahertz (THz) radiation is as high as ∼10% and is spectrally flat. Our measurements are in agreement with finite difference time domain simulations. Such thin metal hole array films allow for very efficient injection of optical…

Reversible Photochemical Control of Doping Levels in Supported Graphene

2017

Controlling the type and density of charge carriers in graphene is vital for a wide range of applications of this material in electronics and optoelectronics. To date, chemical doping and electrostatic gating have served as the two most established means to manipulate the carrier density in graphene. Although highly effective, these two approaches require sophisticated graphene growth or complex device fabrication processes to achieve both the desired nature and the doping densities with generally limited dynamic tunability and spatial control. Here, we report a convenient and tunable optical approach to tune the steady-state carrier density and Fermi energy in graphene by photochemically c…

Bottom-Up, On-Surface-Synthesized Armchair Graphene Nanoribbons for Ultra-High-Power Micro-Supercapacitors

2020

Bottom-up-synthesized graphene nanoribbons (GNRs) with excellent electronic properties are promising materials for energy storage systems. Herein, we report bottom-up-synthesized GNR films employed as electrode materials for micro-supercapacitors (MSCs). The micro-device delivers an excellent volumetric capacitance and an ultra-high power density. The electrochemical performance of MSCs could be correlated with the charge carrier mobility within the differently employed GNRs, as determined by pump–probe terahertz spectroscopy studies.

The Surface of Ice under Equilibrium and Nonequilibrium Conditions

2019

ConspectusThe ice premelt, often called the quasi-liquid layer (QLL), is key for the lubrication of ice, gas uptake by ice, and growth of aerosols. Despite its apparent importance, in-depth understanding of the ice premelt from the microscopic to the macroscopic scale has not been gained. By reviewing data obtained using molecular dynamics (MD) simulations, sum-frequency generation (SFG) spectroscopy, and laser confocal differential interference contrast microscopy (LCM-DIM), we provide a unified view of the experimentally observed variation in quasi-liquid (QL) states. In particular, we disentangle three distinct types of QL states of disordered layers, QL-droplet, and QL-film and discuss…

Back Cover: Nanographenes: Ultrastable, Switchable, and Bright Probes for Super‐Resolution Microscopy (Angew. Chem. Int. Ed. 1/2020)

2019

A new force field including charge directionality for TMAO in aqueous solution

2016

We propose a new force field for trimethylamine N-oxide (TMAO), which is designed to reproduce the long-lived and highly directional hydrogen bond between the TMAO oxygen (OTMAO) atom and surrounding water molecules. Based on the data obtained by ab initio molecular dynamics simulations, we introduce three dummy sites around OTMAO to mimic the OTMAO lone pairs and we migrate the negative charge on the OTMAO to the dummy sites. The force field model developed here improves both structural and dynamical properties of aqueous TMAO solutions. Moreover, it reproduces the experimentally observed dependence of viscosity upon increasing TMAO concentration quantitatively. The simple procedure of the…

Nano-holes vs nano-cracks in thin gold films: What causes anomalous THz transmission?

2015

Nano-structuring materials can change their properties extraordinarily, but so can defects caused by manufacturing. We study the effect of capacitive defects on terahertz transmission in golden nanomeshes, and find their influence crucial.

Surface-Specific Spectroscopy of Water at a Potentiostatically Controlled Supported Graphene Monolayer

2019

Knowledge of the structure of interfacial water molecules at electrified solid materials is the first step toward a better understanding of important processes at such surfaces, in, e.g., electrochemistry, atmospheric chemistry, and membrane biophysics. As graphene is an interesting material with multiple potential applications such as in transistors or sensors, we specifically investigate the graphene–water interface. We use sum-frequency generation spectroscopy to investigate the pH- and potential-dependence of the interfacial water structure in contact with a chemical vapor deposited (CVD) grown graphene surface. Our results show that the SFG signal from the interfacial water molecules a…

Thickness-dependent electron momentum relaxation times in iron films

2020

Terahertz time-domain conductivity measurements in 2 to 100 nm thick iron films resolve the femtosecond time delay between applied electric fields and resulting currents. This current response time decreases from 29 fs for thickest films to 7 fs for the thinnest films. The macroscopic response time is not strictly proportional to the conductivity. This excludes the existence of a single relaxation time universal for all conduction electrons. We must assume a distribution of microscopic momentum relaxation times. The macroscopic response time depends on average and variation of this distribution; the observed deviation between response time and conductivity scaling corresponds to the scaling…

Engineering Proteins at Interfaces: From Complementary Characterization to Material Surfaces with Designed Functions

2018

Abstract Once materials come into contact with a biological fluid containing proteins, proteins are generally—whether desired or not—attracted by the material's surface and adsorb onto it. The aim of this Review is to give an overview of the most commonly used characterization methods employed to gain a better understanding of the adsorption processes on either planar or curved surfaces. We continue to illustrate the benefit of combining different methods to different surface geometries of the material. The thus obtained insight ideally paves the way for engineering functional materials that interact with proteins in a predetermined manner.

Molecular Dynamics Simulations of SFG Librational Modes Spectra of Water at the Water–Air Interface

2016

At the water–air interface, the hydrogen-bond network of water molecules is interrupted, and accordingly, the structure and dynamics of the interfacial water molecules are altered considerably compared with the bulk. Such interfacial water molecules have been studied by surface-specific vibrational sum-frequency generation (SFG) spectroscopy probing high-frequency O–H stretch and H–O–H bending modes. In contrast, the low-frequency librational mode has been much less studied with SFG. Because this mode is sensitive to the hydrogen-bond connectivity, understanding the librational mode of the interfacial water is crucial for unveiling a microscopic view of the interfacial water. Here, we compu…

Nanographene: ultrastabile, schaltbare und helle Sonden für die hochauflösende Mikroskopie

2020

Photoswitchable Micro-Supercapacitor Based on a Diarylethene-Graphene Composite Film

2017

Stimuli-responsive micro-supercapacitors (MSCs) controlled by external stimuli can enable a wide range of applications for future on-chip energy storage. Here, we report on a photoswitchable MSC based on a diarylethene-graphene composite film. The microdevice delivers an outstanding and reversible capacitance modulation of up to 20%, demonstrating a prototype photoswitchable MSC. Terahertz spectroscopy indicates that the photoswitching of the capacitance is enabled by the reversible tuning of interfacial charge injection into diarylethene molecular orbitals, as a consequence of charge transfer at the diarylethene-graphene interface upon light modulation.

Water orientation and hydrogen-bond structure at the fluorite/water interface

2016

AbstractWater in contact with mineral interfaces is important for a variety of different processes. Here, we present a combined theoretical/experimental study which provides a quantitative, molecular-level understanding of the ubiquitous and important CaF2/water interface. Our results show that, at low pH, the surface is positively charged, causing a substantial degree of water ordering. The surface charge originates primarily from the dissolution of fluoride ions, rather than from adsorption of protons to the surface. At high pH we observe the presence of Ca-OH species pointing into the water. These OH groups interact remarkably weakly with the surrounding water and are responsible for the…

Assembly of iron oxide nanosheets at the air-water interface by leucine-histidine peptides

2021

The fabrication of inorganic nanomaterials is important for a wide range of disciplines. While many purely inorganic synthetic routes have enabled a manifold of nanostructures under well-controlled conditions, organisms have the ability to synthesize structures under ambient conditions. For example, magnetotactic bacteria, can synthesize tiny ‘compass needles’ of magnetite (Fe3O4). Here, we demonstrate the bio-inspired synthesis of extended, self-supporting, nanometer-thin sheets of iron oxide at the water–air interface through self-assembly using small histidine-rich peptides.

Nitrated Fatty Acids Modulate the Physical Properties of Model Membranes and the Structure of Transmembrane Proteins

2017

Nitrated fatty acids (NO2 -FAs) act as anti-inflammatory signal mediators, albeit the molecular mechanisms behind NO2 -FAs' influence on diverse metabolic and signaling pathways in inflamed tissues are essentially elusive. Here, we combine fluorescence measurements with surface-specific sum frequency generation vibrational spectroscopy and coarse-grained computer simulations to demonstrate that NO2 -FAs alter lipid organization by accumulation at the membrane-water interface. As the function of membrane proteins strongly depends on both, protein structure as well as membrane properties, we consecutively follow the structural dynamics of an integral membrane protein in presence of NO2 -FAs. …

Size-dependent electron transfer from atomically defined nanographenes to metal oxide nanoparticles.

2020

Atomically defined nanographenes (NGs) feature size-dependent energy gaps induced by, and tuneable through, quantum confinement. Their energy-tunability and robustness make NGs appealing candidates as active elements in sensitized geometries, where NGs functionalize a metal oxide (MO) film with large-area-to-volume ratio. Despite the prominent relevance of NG/MO interfaces for developing novel architectures for solar energy conversion, to date, little information is available regarding the fundamentals of electron transfer (ET) processes taking place from NG donors to MO acceptors. Here, we analyze the interplay between the size of atomically precise NGs and ET dynamics at NG/MO interfaces.…

Rücktitelbild: Nanographene: ultrastabile, schaltbare und helle Sonden für die hochauflösende Mikroskopie (Angew. Chem. 1/2020)

2019

The ultrafast dynamics and conductivity of photoexcited graphene at different Fermi energies

2017

The ultrafast dynamics and conductivity of photoexcited graphene can be explained using solely electronic effects.

Charge transport mechanism in networks of armchair graphene nanoribbons

2020

In graphene nanoribbons (GNRs), the lateral confinement of charge carriers opens a band gap, the key feature to enable novel graphene-based electronics. Successful synthesis of GNRs has triggered efforts to realize field-effect transistors (FETs) based on single ribbons. Despite great progress, reliable and reproducible fabrication of single-ribbon FETs is still a challenge that impedes applications and the understanding of the charge transport. Here, we present reproducible fabrication of armchair GNR-FETs based on a network of nanoribbons and analyze the charge transport mechanism using nine-atom wide and, in particular, five-atom-wide GNRs with unprecedented conductivity. We show formati…

Oberflächenladungen an der CaF 2 ‐Wasser‐Grenzfläche erlauben eine sehr schnelle intermolekulare Übertragung von Schwingungsenergie

2020

Enhanced kinetics of hole transfer and electrocatalysis during photocatalytic oxygen evolution by cocatalyst tuning

2016

Understanding photophysical and electrocatalytic processes during photocatalysis in a powder suspension system is crucial for developing efficient solar energy conversion systems. We report a substantial enhancement by a factor of 3 in photocatalytic efficiency for the oxygen evolution reaction (OER) by adding trace amounts (∼0.05 wt %) of noble metals (Rh and Ru) to a 2 wt % cobalt oxide modified Ta3N5 photocatalyst particulate. The optimized system exhibited high quantum efficiencies (QEs) of up to 28 and 8.4% at 500 and 600 nm in 0.1 M Na2S2O8 at pH 14. By isolation of the electrochemical components to generate doped cobalt oxide electrodes, the electrocatalytic activity of cobalt oxide …

Chemical Vapor Deposition Synthesis and Terahertz Photoconductivity of Low-Band-Gap N = 9 Armchair Graphene Nanoribbons.

2017

Recent advances in bottom-up synthesis of atomically defined graphene nanoribbons (GNRs) with various microstructures and properties have demonstrated their promise in electronic and optoelectronic devices. Here we synthesized N = 9 armchair graphene nanoribbons (9-AGNRs) with a low optical band gap of ∼1.0 eV and extended absorption into the infrared range by an efficient chemical vapor deposition process. Time-resolved terahertz spectroscopy was employed to characterize the photoconductivity in 9-AGNRs and revealed their high intrinsic charge-carrier mobility of approximately 350 cm2·V-1·s-1.

Spin-resolved terahertz spectroscopy

2016

As such, terahertz spectroscopy cannot resolve the spin structure of conducting particles. Here we introduce the spin sensitivity to terahertz spectroscopy by using the spin-valve configuration of the sample. As a result, the number density and momentum scattering time of conduction electrons in a ferromagnetic metal can be resolved according to their spin.

Lipid carbonyl groups terminate the hydrogen bond network of membrane-bound water.

2015

We present a combined experimental sum-frequency generation (SFG) spectroscopy and ab initio molecular dynamics simulations study to clarify the structure and orientation of water at zwitterionic phosphatidylcholine (PC) lipid and amine N-oxide (AO) surfactant monolayers. Simulated O-H stretch SFG spectra of water show good agreement with the experimental data. The SFG response at the PC interface exhibits positive peaks, whereas both negative and positive bands are present for the similar zwitterionic AO interface. The positive peaks at the water/PC interface are attributed to water interacting with the lipid carbonyl groups, which act as efficient hydrogen bond acceptors. This allows the …

Tension Causes Unfolding of Intracellular Vimentin Intermediate Filaments

2020

Intermediate filament (IF) proteins are a class of proteins that constitute different filamentous structures in mammalian cells. As such, IF proteins are part of the load-bearing cytoskeleton and support the nuclear envelope. Molecular dynamics simulations show that IF proteins undergo secondary structural changes to compensate mechanical loads, which is confirmed by experimental in vitro studies on IF hydrogels. However, the structural response of intracellular IF to mechanical load is yet to be elucidated in cellulo. Here, in situ nonlinear Raman imaging combined with multivariate data analysis is used to quantify the intracellular secondary structure of the IF cytoskeletal protein viment…

Kinetic Ionic Permeation and Interfacial Doping of Supported Graphene

2019

Due to its outstanding electrical properties and chemical stability, graphene finds widespread use in various electrochemical applications. Although the presence of electrolytes strongly affects its electrical conductivity, the underlying mechanism has remained elusive. Here, we employ terahertz spectroscopy as a contact-free means to investigate the impact of ubiquitous cations (Li+, Na+, K+, and Ca2+) in aqueous solution on the electronic properties of SiO2-supported graphene. We find that, without applying any external potential, cations can shift the Fermi energy of initially hole-doped graphene by ∼200 meV up to the Dirac point, thus counteracting the initial substrate-induced hole dop…

Membrane Structure of Aquaporin Observed with Combined Experimental and Theoretical Sum Frequency Generation Spectroscopy

2021

High-resolution structural information on membrane proteins is essential for understanding cell biology and for the structure-based design of new medical drugs and drug delivery strategies. X-ray diffraction (XRD) can provide angstrom-level information about the structure of membrane proteins, yet for XRD experiments, proteins are removed from their native membrane environment, chemically stabilized, and crystallized, all of which can compromise the conformation. Here, we describe how a combination of surface-sensitive vibrational spectroscopy and molecular dynamics simulations can account for the native membrane environment. We observe the structure of a glycerol facilitator channel (GlpF)…

Tension causes structural unfolding of intracellular intermediate filaments

2020

AbstractIntermediate filament (IF) proteins are a class of proteins that constitute different filamentous structures in mammalian cells. As such, IF proteins are part of the load-bearing cytoskeleton and support the nuclear envelope. Molecular dynamics simulations have shown that IF proteins undergo secondary structural changes to compensate mechanical loads, which has been confirmed by experimental in vitro studies on IF hydrogels. However, the structural response of intracellular IF to mechanical load has yet to be elucidated in cellulo. Here, we use in situ nonlinear Raman imaging combined with multivariate data analysis to quantify the intracellular secondary structure of the IF cytoske…

Tunable Superstructures of Dendronized Graphene Nanoribbons in Liquid Phase

2019

In this Communication, we report the first synthesis of structurally well-defined graphene nanoribbons (GNRs) functionalized with dendritic polymers. The resultant GNRs possess grafting ratios of 0.59-0.68 for the dendrons of different generations. Remarkably, the precise 3D branched conformation of the grafted dendrons affords the GNRs unprecedented 1D supramolecular self-assembly behavior in tetrahydrofuran (THF), yielding nanowires, helices and nanofibers depending on the dimension of the dendrons. The GNR superstructures in THF exhibit near-infrared absorption with maxima between 650 and 700 nm, yielding an optical bandgap of 1.2-1.3 eV. Ultrafast photoconductivity analyses unveil that …

Dynamical heterogeneities of rotational motion in room temperature ionic liquids evidenced by molecular dynamics simulations

2018

Room temperature ionic liquids (RTILs) have been shown to exhibit spatial heterogeneity or structural heterogeneity in the sense that they form hydrophobic and ionic domains. Yet studies of the relationship between this structural heterogeneity and the ∼picosecond motion of the molecular constituents remain limited. In order to obtain insight into the time scales relevant to this structural heterogeneity, we perform molecular dynamics simulations of a series of RTILs. To investigate the relationship between the structures, i.e., the presence of hydrophobic and ionic domains, and the dynamics, we gradually increase the size of the hydrophobic part of the cation from ethylammonium nitrate (EA…

The role of intact oleosin for stabilization and function of oleosomes.

2013

Lipid storage in plants is achieved among all plant species by formation of oleosomes, enclosing oil (triacylglycerides) in small subcellular droplets. Seeds are rich in this pre-emulsified oil to provide a sufficient energy reservoir for growing. The triacylglyceride core of the oleosomes is surrounded by a phospholipid monolayer containing densely packed proteins called oleosins. They are anchored in the triacylglycerides core with a hydrophobic domain, while the hydrophilic termini remain on the surface. These specialized proteins are expressed during seed development and maturation. Particularly, they play a major role in the stabilization and function of oleosomes. To better understand…

Peptide-Controlled Assembly of Macroscopic Calcium Oxalate Nanosheets

2019

The fabrication of two-dimensional (2D) biomineral nanosheets is of high interest owing to their promise for applications in electronics, filtration, catalysis, and chemical sensing. Using a facile approach inspired by biomineralization in nature, we fabricate laterally macroscopic calcium oxalate nanosheets using β-folded peptides. The template peptides are composed of repetitive glutamic acid and leucine amino acids, self-organized at the air-water interface. Surface-specific sum frequency generation spectroscopy and molecular dynamics simulations reveal that the formation of oxalate nanosheets relies on the peptide-Ca 2+ ion interaction at the interface, which not only restructures the …

Lateral Fusion of Chemical Vapor Deposited N = 5 Armchair Graphene Nanoribbons

2017

Bottom-up synthesis of low-bandgap graphene nanoribbons with various widths is of great importance for their applications in electronic and optoelectronic devices. Here we demonstrate a synthesis of N = 5 armchair graphene nanoribbons (5-AGNRs) and their lateral fusion into wider AGNRs, by a chemical vapor deposition method. The efficient formation of 10- and 15- AGNRs is revealed by a combination of different spectroscopic methods, including Raman and UV−visnear-infrared spectroscopy as well as by scanning tunneling microscopy. The degree of fusion and thus the optical and electronic properties of the resulting GNRs can be controlled by the annealing temperature, providing GNR films with o…

Chemisorption of Atomically Precise 42-Carbon Graphene Quantum Dots on Metal Oxide Films Greatly Accelerates Interfacial Electron Transfer

2019

Graphene quantum dots (GQDs) are emerging as environmentally friendly, low-cost, and highly tunable building blocks in solar energy conversion architectures, such as solar (fuel) cells. Specifically, GQDs constitute a promising alternative for organometallic dyes in sensitized oxide systems. Current sensitized solar cells employing atomically precise GQDs are based on physisorbed sensitizers, with typically limited efficiencies. Chemisorption has been pointed out as a solution to boost photoconversion efficiencies, by allowing improved control over sensitizer surface coverage and sensitizer-oxide coupling strength. Here, employing time-resolved THz spectroscopy, we demonstrate that chemisor…

Nanographenes: Ultrastable, Switchable, and Bright Probes for Super-Resolution Microscopy.

2019

Abstract Super‐resolution fluorescence microscopy has enabled important breakthroughs in biology and materials science. Implementations such as single‐molecule localization microscopy (SMLM) and minimal emission fluxes (MINFLUX) microscopy in the localization mode exploit fluorophores that blink, i.e., switch on and off, stochastically. Here, we introduce nanographenes, namely large polycyclic aromatic hydrocarbons that can also be regarded as atomically precise graphene quantum dots, as a new class of fluorophores for super‐resolution fluorescence microscopy. Nanographenes exhibit outstanding photophysical properties: intrinsic blinking even in air, excellent fluorescence recovery, and sta…

A Highly Luminescent Nitrogen-Doped Nanographene as an Acid- and Metal-Sensitive Fluorophore for Optical Imaging.

2021

Dibenzo[hi,st]ovalene (DBOV) has excellent photophysical properties, including strong fluorescence and high ambient stability. Moreover, the optical blinking properties of DBOV have enabled optical super-resolution single-molecule localization microscopy with an imaging resolution beyond the diffraction limit. Various organic and inorganic fluorescent probes have been developed for super-resolution imaging, but those sensitive to pH and/or metal ions have remained elusive. Here, we report a diaza-derivative of DBOV (N-DBOV), synthesized in eight steps with a total yield of 15%. Nitrogen (N)-bearing zigzag edges were formed through oxidative cyclization of amino groups in the last step. UV-v…

Surface charges at the CaF2/water interface allow very fast intermolecular vibrational-energy transfer

2020

Abstract We investigate the dynamics of water in contact with solid calcium fluoride, where at low pH, localized charges can develop upon fluorite dissolution. We use 2D surface‐specific vibrational spectroscopy to quantify the heterogeneity of the interfacial water (D2O) molecules and provide information about the sub‐picosecond vibrational‐energy‐relaxation dynamics at the buried solid/liquid interface. We find that strongly H‐bonded OD groups, with a vibrational frequency below 2500 cm−1, display very rapid spectral diffusion and vibrational relaxation; for weakly H‐bonded OD groups, above 2500 cm−1, the dynamics slows down substantially. Atomistic simulations based on electronic‐structu…

Synthesis of Nonplanar Graphene Nanoribbon with Fjord Edges

2021

As a new family of semiconductors, graphene nanoribbons (GNRs), nanometer-wide strips of graphene, have appeared as promising candidates for next-generation nanoelectronics. Out-of-plane deformation of π-frames in GNRs brings further opportunities for optical and electronic property tuning. Here we demonstrate a novel fjord-edged GNR (FGNR) with a nonplanar geometry obtained by regioselective cyclodehydrogenation. Triphenanthro-fused teropyrene 1 and pentaphenanthro-fused quateropyrene 2 were synthesized as model compounds, and single-crystal X-ray analysis revealed their helically twisted conformations arising from the [5]helicene substructures. The structures and photophysical properties …

Single-crystal I h ice surfaces unveil connection between macroscopic and molecular structure

2017

Physics and chemistry of ice surfaces are not only of fundamental interest but also have important impacts on biological and environmental processes. As ice surfaces—particularly the two prism faces—come under greater scrutiny, it is increasingly important to connect the macroscopic faces with the molecular-level structure. The microscopic structure of the ubiquitous ice Ih crystal is well-known. It consists of stacked layers of chair-form hexagonal rings referred to as molecular hexagons. Crystallographic unit cells can be assembled into a regular right hexagonal prism. The bases are labeled crystallographic hexagons. The two hexagons are rotated 30° with respect to each other. The linkage…

Hysteresis in graphene nanoribbon field-effect devices

2020

Hysteresis in the current response to a varying gate voltage is a common spurious effect in carbon-based field effect transistors. Here, we use electric transport measurements to probe the charge transport in networks of armchair graphene nanoribbons with a width of either 5 or 9 carbon atoms, synthesized in a bottom-up approach using chemical vapor deposition. Our systematic study on the hysteresis of such graphene nanoribbon transistors, in conjunction with temperature-dependent transport measurements shows that the hysteresis can be fully accounted for by trapping/detrapping carriers in the SiO2 layer. We extract the trap densities and depth, allowing us to identify shallow traps as the …

Efficient Hot Electron Transfer in Quantum Dot-Sensitized Mesoporous Oxides at Room Temperature

2018

Hot carrier cooling processes represent one of the major efficiency losses in solar energy conversion. Losses associated with cooling can in principle be circumvented if hot carrier extraction toward selective contacts is faster than hot carrier cooling in the absorber (in so-called hot carrier solar cells). Previous work has demonstrated the possibility of hot electron extraction in quantum dot (QD)-sensitized systems, in particular, at low temperatures. Here we demonstrate a room-temperature hot electron transfer (HET) with up to unity quantum efficiency in strongly coupled PbS quantum dot-sensitized mesoporous SnO2. We show that the HET efficiency is determined by a kinetic competition b…

Ab Initio Liquid Water Dynamics in Aqueous TMAO Solution

2015

Ab initio molecular dynamics (AIMD) simulations in trimethylamine N-oxide (TMAO)-D2O solution are employed to elucidate the effects of TMAO on the reorientational dynamics of D2O molecules. By decomposing the O-D groups of the D2O molecules into specific subensembles, we reveal that water reorientational dynamics are retarded considerably in the vicinity of the hydrophilic TMAO oxygen (O(TMAO)) atom, due to the O-D···O(TMAO) hydrogen-bond. We find that this reorientational motion is governed by two distinct mechanisms: The O-D group rotates (1) after breaking the O-D···O(TMAO) hydrogen-bond, or (2) together with the TMAO molecule while keeping this hydrogen-bond intact. While the orientatio…

Accessing the fundamentals of magnetotransport in metals with terahertz probes

2015

Spin-dependent conduction in metals underlies all modern magnetic memory technologies, such as giant magnetoresistance (GMR). The charge current in ferromagnetic transition metals is carried by two non-mixing populations of sp-band Fermi-level electrons: one of majority-spin and one of minority-spin. These electrons experience spin-dependent momentum scattering with localized electrons, which originate from the spin-split d-band. The direct observation of magnetotransport under such fundamental conditions, however, requires magnetotransport measurements on the same timescale as the electron momentum scattering, which takes place in the sub-100 fs regime. Using terahertz electromagnetic prob…

CCDC 2058017: Experimental Crystal Structure Determination

2021

Related Article: Xuelin Yao, Wenhao Zheng, Silvio Osella, Zijie Qiu, Shuai Fu, Dieter Schollmeyer, Beate Müller, David Beljonne, Mischa Bonn, Hai I. Wang, Klaus Müllen, Akimitsu Narita|2021|J.Am.Chem.Soc.|143|5654|doi:10.1021/jacs.1c01882

CCDC 2058018: Experimental Crystal Structure Determination

2021

Related Article: Xuelin Yao, Wenhao Zheng, Silvio Osella, Zijie Qiu, Shuai Fu, Dieter Schollmeyer, Beate Müller, David Beljonne, Mischa Bonn, Hai I. Wang, Klaus Müllen, Akimitsu Narita|2021|J.Am.Chem.Soc.|143|5654|doi:10.1021/jacs.1c01882