Controlled Bipolar Doping of One-Dimensional van der Waals Nb2Pd3Se8.

Tailoring the electrical properties of one-dimensional (1D) van der Waals (vdW) materials is desirable for their applications toward electronic devices by exploiting their unique characteristics. However, 1D vdW materials have not been extensively investigated for modulation of their electrical properties. Here we control doping levels and types of 1D vdW Nb2Pd3Se8 over a wide energy range by immersion in AuCl3 or ß-nicotinamide adenine dinucleotide (NADH) solutions, respectively. Through spectroscopic analyses and electrical characterizations, we confirm that the charges were effectively transferred to Nb2Pd3Se8, and the dopant concentration was adjusted to the immersion time. Furthermore, we make the axial p-n junction of 1D Nb2Pd3Se8 by a selective area p-doping using the AuCl3 solution, which exhibits rectifying behavior with an Iforward/Ireverse of 81 and an ideality factor of 1.2. Our findings could pave the way to more practical and functional electronic devices based on 1D vdW materials.

Carrier mobility of one-dimensional vanadium selenide (V2Se9) monolayer and nanoribbon systems: DFT study.

Vanadium selenide (V2Se9) is a true one-dimensional (1D) crystal composed of atomic nanochains bonded by van der Waals (vdW) interactions. Recent experiments revealed the mechanical exfoliation of newly synthesized V2Se9. In this study, we predicted the electronic and transport properties of V2Se9through computational analyses. We calculated the intrinsic carrier mobility of V2Se9monolayers (MLs) and nanoribbons (NRs) using density functional theory and deformation potential theory. We found that the electron mobility of the two-dimensional (2D) (010)-plane ML of V2Se9is highly anisotropic, reachingµ2D,ze=1327cm2V-1s-1across the chain direction. The electron mobility of 1D NR systems in a (010)-plane ML of V2Se9along the chain direction continuously increased as the thickness increased from 1-chain to 4-chain NR (width below 3 nm). Interestingly, the electron mobility of 1D 4-chain NR along the chain direction (µ1D,xe=775cm2V-1s-1) was higher than that of a 2D (010)-plane ML (µ2D,xe=567cm2V-1s-1). These results demonstrate the potential of vdW-1D crystal V2Se9as a new nanomaterial for ultranarrow (sub-3 nm width) optoelectronic devices with high electron mobility.

Connection between the time distribution and length scale of dynamic heterogeneity explored by probe reorientations of different sizes.

The rotational dynamics of fluorescent probes of different sizes in glass-forming materials were examined to correlate the time distribution and length scale of the dynamic heterogeneity (ξhet). As the size of the probe increased, the temperature dependence of the rotation correlation time (τc) shifted to longer times, and from this shift, the length scale associated with the glass transition (ξα) was estimated through the Debye-Stokes-Einstein (DSE) relationship and the length scale of the probe (ξsDFT) estimated from quantum mechanical calculations. The estimated ξα values roughly matched with ξhet obtained from calorimetric analysis but were considerably smaller than those deduced from 4D NMR, boson peak, and four-point dynamic susceptibility measurements but with a similar trend of decrease in the length scale upon the increase in the stretching exponent (ß) of the system. Because ß of the glass formers represents the time distribution of the system, and τc is related to the weighted average of the distribution, the length-scale distribution of the glass transition can be deduced by adopting the DSE relationship and assuming ξα is the weighted average of this distribution at the glass transition temperature. In such a case, the upper bound of the length scale and trend matches the experimentally obtained ξhet from 4D NMR, boson peak, and four-point dynamic susceptibility measurements. Furthermore, at a given temperature, as the probe size increased, the ß value reported by the probe increased, whereas the temperature dependence of ß, which strongly correlates with the fragility of the system, was independent of the probe size.

Ta2 Ni3 Se8 : 1D van der Waals Material with Ambipolar Behavior.

In this study, high-purity and centimeter-scale bulk Ta2 Ni3 Se8 crystals are obtained by controlling the growth temperature and stoichiometric ratio between tantalum, nickel, and selenium. It is demonstrated that the bulk Ta2 Ni3 Se8 crystals could be effectively exfoliated into a few chain-scale nanowires through simple mechanical exfoliation and liquid-phase exfoliation. Also, the calculation of electronic band structures confirms that Ta2 Ni3 Se8 is a semiconducting material with a small bandgap. A field-effect transistor is successfully fabricated on the mechanically exfoliated Ta2 Ni3 Se8 nanowires. Transport measurements at room temperature reveal that Ta2 Ni3 Se8 nanowires exhibit ambipolar semiconducting behavior with maximum mobilities of 20.3 and 3.52 cm2 V-1 s-1 for electrons and holes, respectively. The temperature-dependent transport measurement (from 90 to 295 K) confirms the carrier transport mechanism of Ta2 Ni3 Se8 nanowires. Based on these characteristics, the obtained 1D vdW material is expected to be a potential candidate for additional 1D materials as channel materials.

Connection between BosonSampling with quantum and classical input states.

BosonSampling is a problem of sampling events according to the transition probabilities of indistinguishable photons in a linear optical network. Computational hardness of BosonSampling depends on photon-number statistics of the input light. BosonSampling with multi-photon Fock states at the input is believed to be classically intractable but there exists an efficient classical algorithm for classical input states. In this paper, we present a mathematical connection between BosonSampling with quantum and classical light inputs. Specifically, we show that the generating function of a transition probability for Fock-state BosonSampling (FBS) can be expressed as a transition probability of thermal-light inputs. The closed-form expression of a thermal-light transition probability allows all possible transition probabilities of FBS to be obtained by calculating a single matrix permanent. Moreover, the transition probability of FBS is shown to be expressed as an integral involving a Gaussian function multiplied by a Laguerre polynomial, resulting in a fast oscillating integrand. Our work sheds new light on computational hardness of FBS by identifying the mathematical connection between BosonSampling with quantum and classical light.

Entangling bosons through particle indistinguishability and spatial overlap.

Particle identity and entanglement are two fundamental quantum properties that work as major resources for various quantum information tasks. However, it is still a challenging problem to understand the correlation of the two properties in the same system. While recent theoretical studies have shown that the spatial overlap between identical particles is necessary for nontrivial entanglement, the exact role of particle indistinguishability in the entanglement of identical particles has never been analyzed quantitatively before. Here, we theoretically and experimentally investigate the behavior of entanglement between two bosons as spatial overlap and indistinguishability simultaneously vary. The theoretical computation of entanglement for generic two bosons with pseudospins is verified experimentally in a photonic system. Our results show that the amount of entanglement is a monotonically increasing function of both quantities. We expect that our work provides an insight into deciphering the role of the entanglement in quantum networks that consist of identical particles.

Tuning the electronic properties of highly anisotropic 2D dangling-bond-free sheets from 1D V2Se9 chain structures.

True one-dimensional (1D) van der Waals materials can form two-dimensional (2D) dangling-bond-free anisotropic surfaces. Dangling bonds on surfaces act as defects for transporting charge carriers. In this study, we consider true 1D materials to be V2Se9 chains, and then the electronic structures of 2D sheets composed of true 1D V2Se9 chains are calculated. The (010) plane has indirect bandgap with 0.757 eV (1.768 eV), while the (111̅) plane shows a nearly direct bandgap of 1.047 eV (2.118 eV) for DFT-D3 (HSE06) correction, respectively. The (111̅) plane of V2Se9 is expected to be used in optoelectronic devices because it contains a nearly direct bandgap. Partial charge analysis indicates that the (010) plane exhibits interchain interaction is stronger than the (111̅) plane. To investigate the strain effect, we increased the interchain distance of planes until an indirect-to-direct bandgap transition occurred. The (010) plane then demonstrated a direct bandgap when interchain distance increased by 30%, while the (111̅) plane demonstrated a direct bandgap when the interchain distance increased by 10%. In mechanical sensors, this change in the bandgap was induced by the interchain distance.

Proposal for Microwave Boson Sampling.

Boson sampling, the task of sampling the probability distribution of photons at the output of a photonic network, is believed to be hard for any classical device. Unlike other models of quantum computation that require thousands of qubits to outperform classical computers, boson sampling requires only a handful of single photons. However, a scalable implementation of boson sampling is missing. Here, we show how superconducting circuits provide such platform. Our proposal differs radically from traditional quantum-optical implementations: rather than injecting photons in waveguides, making them pass through optical elements like phase shifters and beam splitters, and finally detecting their output mode, we prepare the required multiphoton input state in a superconducting resonator array, control its dynamics via tunable and dispersive interactions, and measure it with nondemolition techniques.

Fast delocalization leads to robust long-range excitonic transfer in a large quantum chlorosome model.

Chlorosomes are efficient light-harvesting antennas containing up to hundreds of thousands of bacteriochlorophyll molecules. With massively parallel computer hardware, we use a nonperturbative stochastic Schrödinger equation, while including an atomistically derived spectral density, to study excitonic energy transfer in a realistically sized chlorosome model. We find that fast short-range delocalization leads to robust long-range transfer due to the antennae's concentric-roll structure. Additionally, we discover anomalous behavior arising from different initial conditions, and outline general considerations for simulating excitonic systems on the nanometer to micrometer scale.

Atomistic study of energy funneling in the light-harvesting complex of green sulfur bacteria.

Phototrophic organisms such as plants, photosynthetic bacteria, and algae use microscopic complexes of pigment molecules to absorb sunlight. Within the light-harvesting complexes, which frequently have several functional and structural subunits, the energy is transferred in the form of molecular excitations with very high efficiency. Green sulfur bacteria are considered to be among the most efficient light-harvesting organisms. Despite multiple experimental and theoretical studies of these bacteria, the physical origin of the efficient and robust energy transfer in their light-harvesting complexes is not well understood. To study excitation dynamics at the systems level, we introduce an atomistic model that mimics a complete light-harvesting apparatus of green sulfur bacteria. The model contains approximately 4000 pigment molecules and comprises a double wall roll for the chlorosome, a baseplate, and six Fenna-Matthews-Olson trimer complexes. We show that the fast relaxation within functional subunits combined with the transfer between collective excited states of pigments can result in robust energy funneling to the initial excitation conditions and temperature changes. Moreover, the same mechanism describes the coexistence of multiple time scales of excitation dynamics frequently observed in ultrafast optical experiments. While our findings support the hypothesis of supertransfer, the model reveals energy transport through multiple channels on different length scales.

Theoretical characterization of excitation energy transfer in chlorosome light-harvesting antennae from green sulfur bacteria.

We present a theoretical study of excitation dynamics in the chlorosome antenna complex of green photosynthetic bacteria based on a recently proposed model for the molecular assembly. Our model for the excitation energy transfer (EET) throughout the antenna combines a stochastic time propagation of the excitonic wave function with molecular dynamics simulations of the supramolecular structure and electronic structure calculations of the excited states. We characterized the optical properties of the chlorosome with absorption, circular dichroism and fluorescence polarization anisotropy decay spectra. The simulation results for the excitation dynamics reveal a detailed picture of the EET in the chlorosome. Coherent energy transfer is significant only for the first 50 fs after the initial excitation, and the wavelike motion of the exciton is completely damped at 100 fs. Characteristic time constants of incoherent energy transfer, subsequently, vary from 1 ps to several tens of ps. We assign the time scales of the EET to specific physical processes by comparing our results with the data obtained from time-resolved spectroscopy experiments.

A stochastic reorganizational bath model for electronic energy transfer.

Environmentally induced fluctuations of the optical gap play a crucial role in electronic energy transfer dynamics. One of the simplest approaches to incorporate such fluctuations in energy transfer dynamics is the well known Haken-Strobl-Reineker (HSR) model, in which the energy-gap fluctuation is approximated as white noise. Recently, several groups have employed molecular dynamics simulations and excited-state calculations in conjunction to account for excitation energies' thermal fluctuations. On the other hand, since the original work of HSR, many groups have employed stochastic models to simulate the same transfer dynamics. Here, we discuss a rigorous connection between the stochastic and the atomistic bath models. If the phonon bath is treated classically, time evolution of the exciton-phonon system can be described by Ehrenfest dynamics. To establish the relationship between the stochastic and atomistic bath models, we employ a projection operator technique to derive the generalized Langevin equations for the energy-gap fluctuations. The stochastic bath model can be obtained as an approximation of the atomistic Ehrenfest equations via the generalized Langevin approach. Based on this connection, we propose a novel scheme to take account of reorganization effects within the framework of stochastic models. The proposed scheme provides a better description of the population dynamics especially in the regime of strong exciton-phonon coupling. Finally, we discuss the effect of the bath reorganization in the absorption and fluorescence spectra of ideal J-aggregates in terms of the Stokes shifts. We find a simple expression that relates the reorganization contribution to the Stokes shifts - the reorganization shift - to the ideal or non-ideal exciton delocalization in a J-aggregate. The reorganization shift can be described by three parameters: the monomer reorganization energy, the relaxation time of the optical gap, and the exciton delocalization length. This simple relationship allows one to understand the physical origin of the Stokes shifts in molecular aggregates.

Temperature and carbon assimilation regulate the chlorosome biogenesis in green sulfur bacteria.

Green photosynthetic bacteria adjust the structure and functionality of the chlorosome-the light-absorbing antenna complex-in response to environmental stress factors. The chlorosome is a natural self-assembled aggregate of bacteriochlorophyll (BChl) molecules. In this study, we report the regulation of the biogenesis of the Chlorobaculum tepidum chlorosome by carbon assimilation in conjunction with temperature changes. Our studies indicate that the carbon source and thermal stress culture of C. tepidum grows slower and incorporates fewer BChl c in the chlorosome. Compared with the chlorosome from other cultural conditions we investigated, the chlorosome from the carbon source and thermal stress culture displays (a) smaller cross-sectional radius and overall size, (b) simplified BChl c homologs with smaller side chains, (c) blue-shifted Qy absorption maxima, and (d) a sigmoid-shaped circular dichroism spectra. Using a theoretical model, we analyze how the observed spectral modifications can be associated with structural changes of BChl aggregates inside the chlorosome. Our report suggests a mechanism of metabolic regulation for chlorosome biogenesis.

BoostSweet: Learning molecular perceptual representations of sweeteners.

The development of safe artificial sweeteners has attracted considerable interest in the food industry. Previous machine learning (ML) studies based on quantitative structure-activity relationships have provided some molecular principles for predicting sweetness, but these models can be improved via the chemical recognition of sweetness active factors. Our ML model, a soft-vote ensemble model that has a light gradient boosting machine and uses both layered fingerprints and alvaDesc molecular descriptor features, demonstrates state-of-the-art performance, with an AUROC score of 0.961. Based on an analysis of feature importance and dataset, we identified that the number of nitrogen atoms that serve as hydrogen bond donors in molecules can play an essential role in determining sweetness. These results potentially provide an advanced understanding of the relationship between molecular structure and sweetness, which can be used to design new sweeteners based on molecular structural dependence.

Unveiling two-dimensional magnesium hydride as a hydrogen storage material via a generative adversarial network.

This study used an artificial intelligence (AI)-based crystal inverse-design approach to investigate the new phase of two-dimensional (2D) pristine magnesium hydride (Mg x H y ) sheets and verify their availability as a hydrogen storage medium. A 2D binary phase diagram for the generated crystal images was constructed, which was used to identify significant 2D crystal structures. Then, the electronic and dynamic properties of the Mg x H y sheets in low-energy periodic phases were identified via density functional theory (DFT) calculations; this revealed a previously unknown phase of 2D MgH2 with a P4̄m2 space group. In the proposed structure, the adsorption behaviors of the Li-decorated system were investigated for multiple hydrogen molecules. It was confirmed that Li-decorated MgH2 has an expected theoretical gravimetric density of 6 wt%, with an average H2 adsorption energy of -0.105 eV. Therefore, it is anticipated that P4̄m2 MgH2 sheets can be employed effectively as a medium for hydrogen storage. Additionally, this finding indicates that a deep learning-based approach is beneficial for exploring unrevealed 2D materials.

Midwavelength Infrared Colloidal Nanowire Laser.

Realizing bright colloidal infrared emitters in the midwavelength infrared (or mid-IR), which can be used for low-power IR light-emitting diodes (LEDs), sensors, and deep-tissue imaging, has been a challenge for the last few decades. Here, we present colloidal tellurium nanowires with strong emission intensity at room temperature and even lasing at 3.6 µm (ω) under cryotemperature. Furthermore, the second-harmonic field at 1.8 µm (2ω) and the third-harmonic field at 1.2 µm (3ω) are successfully generated thanks to the intrinsic property of the tellurium nanowire. These unique optical features have never been reported for colloidal tellurium nanocrystals. With the colloidal midwavelength infrared (MWIR) Te nanowire laser, we demonstrate its potential in biomedical applications. MWIR lasing has been clearly observed from nanowires embedded in a human neuroblastoma cell, which could further realize deep-tissue imaging and thermotherapy in the near future.

Additive-free photo-mediated oxidative cyclization of pyridinium acylhydrazones to 1,3,4-oxadiazoles: solid-state conversion in a microporous organic polymer and supramolecular energy-level engineering.

We discovered the efficient catalyst-free, photo-mediated oxidative cyclization reaction of bis-p-pyridinium benzoyl hydrazone (BH1) to 2-pyridinium-5-phenyl-1,3,4-oxadiazoles. This photoreaction is remarkable because it does not require additives (e.g., bases, strong oxidants, or photocatalysts), which are essential in previous reports, and proceeds very effectively even with solid-state microporous organic polymers. Interestingly, we found that the inclusion complexation of BH1 with cucurbit[7]uril (CB7) interferes with the photo-induced electron transfer from BH1 to molecular oxygen through modification of the LUMO energy level, thus inhibiting the photo-medicated oxidative cyclization.

Unveiling the role of micropores in porous carbon for Li-S batteries using operando SAXS.

The movement of the sulfur species of a lithium-sulfur battery cathode was directly observed through pioneering operando SAXS analysis. Micropore is a prior repository for sulfur before and after the electrochemical reaction. Mesopore is actual reaction site for sulfur species. The separate properties of the pores were established, adding critical insight to advanced carbon cathode material design.

Theoretical Study of Anisotropic Carrier Mobility for Two-Dimensional Nb2Se9 Material.

Finding new materials with satisfying all the desired criteria for nanodevices is an extremely difficult work. Here, we introduce a novel Nb2Se9 material as a promising candidate, capable of overcoming some physical limitations, such as a suitable band gap, high carrier mobility, and chemical stability. Unlike graphene, it has a noticeable band gap and no dangling bonds at surfaces that deteriorate transport properties, owing to its molecular chain structure. Using density functional theory (DFT) calculations with deformation potential (DP) theory, we find that the electron mobility of 2D Nb2Se9 across the axis direction reaches up to 2.56 × 103 cm2 V-1 s-1 and is approximately 2.5-6 times higher than the mobility of other 2D materials, such as MoS2, black phosphorous, and InSe, at room temperature. Moreover, the mobility of 2D Nb2Se9 is highly anisotropic (µ a /µ c ≈ 6.5). We demonstrate the potential of 2D Nb2Se9 for applications in nanoscale electronic devices and, possibly, mid-infrared photodetectors.

One-dimensional van der Waals stacked p-type crystal Ta2Pt3Se8 for nanoscale electronics.

Recently, ternary transition metal chalcogenides Ta2X3Se8 (X = Pd or Pt) have attracted great interest as a class of emerging one-dimensional (1D) van der Waals (vdW) materials. In particular, Ta2Pd3Se8 has been actively studied owing to its excellent charge transport properties as an n-type semiconductor and ultralong ballistic phonon transport properties. Compared to subsequent studies on the Pd-containing material, Ta2Pt3Se8, another member of this class of materials has been considerably less explored despite its promising electrical properties as a p-type semiconductor. Herein, we demonstrate the electrical properties of Ta2Pt3Se8 as a promising channel material for nanoelectronic applications. High-quality bulk Ta2Pt3Se8 single crystals were successfully synthesized by a one-step vapor transport reaction. Scanning Kelvin probe microscopy measurements were used to investigate the surface potential difference and work function of the Ta2Pt3Se8 nanoribbons of various thicknesses. Field-effect transistors fabricated on exfoliated Ta2Pt3Se8 nanoribbons exhibited moderate p-type transport properties with a maximum hole mobility of 5 cm2 V-1 s-1 and an Ion/Ioff ratio of >104. Furthermore, the charge transport mechanism of Ta2Pt3Se8 was analyzed by temperature-dependent transport measurements in the temperature range from 90 to 320 K. To include Ta2Pt3Se8 in a building block for modern 1D electronics, we demonstrate p-n junction characteristics using the electron beam doping method.