First-Principles Study of Honeycomb Borophene on the Mo₂C Substrate

Honeycomb borophene (HB) is an important building block for diverse quantum phase observation and applications. However, freestanding HB is energetically unstable, resulting from electron deficiency. Based on a comprehensive first-principles study, we herein predict that the Mo2C monolayer can serve as an effective two-dimensional substrate to prepare planar HB. It is found that the planar HB layer is energetically favorable on the Mo2C substrate with desirable thermal and dynamical stabilities, benefiting from suitable interfacial interactions and electron transfer from Mo2C to HB. In addition, HB is found to be an effective buffer layer to decouple the electronic interactions and modify metal–semiconductor contact. These insightful results not only indicate that the Mo2C substrate is a promising alternative to synthesizing a stable borophene monolayer with pure honeycomb lattice but also provide hints for applications of HB-based materials in high-performance miniaturized electronic devices

Study of Electronic Structures and Pigment–Protein Interactions in the Reaction Center of Thermochromatium tepidum with a Dynamic Environment

On the basis of the recently reported X-ray crystal structure of light-harvesting complex 1–reaction center (LH1-RC) complex from <i>Thermochromatium tepidum</i>, we investigate electronic structures and pigment–protein interactions in the RC complex from a theoretical perspective. Hybrid quantum-mechanics/molecular-mechanics methods in combination with molecular dynamics simulations are employed to study environmental effects on excitation energies of RC cofactors with the consideration of a dynamic environment. The environmental effects are found to be essential for electronic structure determination. The special pair, a dimer of bacteriochlorophylls which serves as the primary electron donor in the bacterial RC, is our focus in this work. The first excited state of the special pair is found to have the lowest excitation energy of all molecules in the system, making it the most likely populated site after the excitation transfer. The transition charges from electrostatic potentials and the point dipole approximation have been applied to calculate the electronic coupling between individual pigments and that between the special pair and other pigments. Stronger electronic coupling is obtained between the P_M molecule and the L branch pigments than that between the P_M and the pigments in the M branch. Quantum chemical calculations reveal charge transfer characteristics of the first excited state of the special pair. It follows that charge separation takes place along the L branch in the RC. Spectral densities for all the cofactors are also calculated

Intrinsic Ferroelectric Quantum Spin Hall Insulator in Monolayer Na₃Bi with Surface Trimerization

Two-dimensional (2D) ferroelectric quantum spin Hall (FEQSH) insulator, which features coexisting ferroelectric and topologically insulating orders in two-dimension, is generally considered available only in engineered 2D systems. This is detrimental to the synthesis and application of next generation nonvolatile functional candidates. Therefore, exploring the intrinsic 2D FEQSH insulator is crucial. Here, by means of first-principles, we report a long-thought intrinsic 2D FEQSH insulator in monolayer Na3Bi with surface trimerization. The material harbors merits including large ferroelectric polarization, sizable nontrivial band gap, and low switching barrier, which are particularly beneficial for the detection and observation of ferroelectric topologically insulating states. Also, it is capable of nonvolatile switching of nontrivial spin textures via inherent ferroelectricity. The fantastic combination of excellent ferroelectric and topological phases in intrinsic the Na3Bi monolayer serves as an alluring platform for accelerating both scientific discoveries and innovative applications

Plasmon-Enhanced Exciton Delocalization in Squaraine-Type Molecular Aggregates

Enlarging exciton coherence lengths in molecular aggregates is critical for enhancing the collective optical and transport properties of molecular thin film nanostructures or devices. We demonstrate that the exciton coherence length of squaraine aggregates can be increased from 10 to 24 molecular units at room temperature when preparing the aggregated thin film on a metallic rather than a dielectric substrate. Two-dimensional electronic spectroscopy measurements reveal a much lower degree of inhomogeneous line broadening for aggregates on a gold film, pointing to a reduced disorder. The result is corroborated by simulations based on a Frenkel exciton model including exciton–plasmon coupling effects. The simulation shows that localized, energetically nearly resonant excitons on spatially well separated segments can be radiatively coupled via delocalized surface plasmon polariton modes at a planar molecule–gold interface. Such plasmon-enhanced delocalization of the exciton wave function is of high importance for improving the coherent transport properties of molecular aggregates on the nanoscale. Additionally, it may help tailor the collective optical response of organic materials for quantum optical applications

Charge Delocalization and Vibronic Couplings in Quadrupolar Squaraine Dyes

Squaraines are prototypical quadrupolar charge-transfer chromophores that have recently attracted much attention as building blocks for solution-processed photovoltaics, fluorescent probes with large two-photon absorption cross sections, and aggregates with large circular dichroism. Their optical properties are often rationalized in terms of phenomenological essential state models, considering the coupling of two zwitterionic excited states to a neutral ground state. As a result, optical transitions to the lowest S1 excited state are one-photon allowed, whereas the next higher S2 state can only be accessed by two-photon transitions. A further implication of these models is a substantial reduction of vibronic coupling to the ubiquitous high-frequency vinyl-stretching modes of organic materials. Here, we combine time-resolved vibrational spectroscopy, two-dimensional electronic spectroscopy, and quantum-chemical simulations to test and rationalize these predictions for nonaggregated molecules. We find small Huang–Rhys factors below 0.01 for the high-frequency, 1500 cm–1 modes in particular, as well as a noticeable reduction for those of lower frequency modes in general for the electronic S0 → S1 transition. The two-photon allowed state S2 is well separated energetically from S1 and has weak vibronic signatures as well. Thus, the resulting pronounced concentration of the oscillator strength in a narrow region relevant to the lowest electronic transition makes squaraines and their aggregates exceptionally interesting for strong and ultrastrong coupling of excitons to localized light modes in external resonators with chiral properties that can largely be controlled by the molecular architecture

Wavy Two-Dimensional Conjugated Metal–Organic Framework with Metallic Charge Transport

Two-dimensional conjugated metal–organic frameworks (2D c-MOFs) have emerged as a new class of crystalline layered conducting materials that hold significant promise for applications in electronics and spintronics. However, current 2D c-MOFs are mainly made from organic planar ligands, whereas layered 2D c-MOFs constructed by curved or twisted ligands featuring novel orbital structures and electronic states remain less developed. Herein, we report a Cu-catecholate wavy 2D c-MOF (Cu3(HFcHBC)2) based on a fluorinated core-twisted contorted hexahydroxy-hexa-cata-hexabenzocoronene (HFcHBC) ligand. We show that the resulting film is composed of rod-like single crystals with lengths up to ∼4 μm. The crystal structure is resolved by high-resolution transmission electron microscopy (HRTEM) and continuous rotation electron diffraction (cRED), indicating a wavy honeycomb lattice with AA-eclipsed stacking. Cu3(HFcHBC)2 is predicted to be metallic based on theoretical calculation, while the crystalline film sample with numerous grain boundaries apparently exhibits semiconducting behavior at the macroscopic scale, characterized by obvious thermally activated conductivity. Temperature-dependent electrical conductivity measurements on the isolated single-crystal devices indeed demonstrate the metallic nature of Cu3(HFcHBC)2, with a very weak thermally activated transport behavior and a room-temperature conductivity of 5.2 S cm–1. Furthermore, the 2D c-MOFs can be utilized as potential electrode materials for energy storage, which display decent capacity (163.3 F g–1) and excellent cyclability in an aqueous 5 M LiCl electrolyte. Our work demonstrates that wavy 2D c-MOF using contorted ligands are capable of intrinsic metallic transport, marking the emergence of new conductive MOFs for electronic and energy applications