Polymerization Improvement of Graphitic Carbon Nitride Films Derived from Melamine and Thiourea.

Deposition of low-cost, efficient, and environmentally friendly graphitic carbon nitride (g-CN) films as photoanodes is a crucial step for constructing photoelectrochemical (PEC) cells and exploring their PEC performance. Currently, the improvement of the photocurrent density of g-CN films is badly needed for their practical applications in PEC water splitting. Enhancing the g-CN crystallinity by optimizing their synthesis conditions only through screening appropriate reactant precursors is insufficient for this purpose.

An improved DIIS method using a versatile residual matrix to accelerate SCF starting from a crude guess.

The minimization of the commutator of the Fock and density matrices as the error matrix in the direct inversion of the iterative subspace (CDIIS) developed by Pulay is a powerful self-consistent field (SCF) acceleration technique for the construction of optimum Fock matrix, if initiated with a fair initial guess. In this work, we present an alternative minimized error matrix to the commutator in the CDIIS, namely the residual or the gradient of the energy-functional for a Slater determinant subject to the orthonormality constraints among orbitals, representing the search for a newly improved Fock matrix in the direction of the residual in the direct inversion of the iterative subspace (RDIIS). Implemented in the computational chemistry package GAMESS, the RDIIS is compared with the standard CDIIS and the second order SCF orbital optimization (SOSCF) for tested molecules started with a crude guess.

Moiré magnetic exchange interactions in twisted magnets.

In addition to moiré superlattices, twisting can also generate moiré magnetic exchange interactions (MMEIs) in van der Waals magnets. However, owing to the extreme complexity and twist-angle-dependent sensitivity, all existing models fail to fully capture MMEIs and thus cannot provide an understanding of MMEI-induced physics. Here, we develop a microscopic moiré spin Hamiltonian that enables the effective description of MMEIs via a sliding-mapping approach in twisted magnets, as demonstrated in twisted bilayer CrI.

Controlling Charge Carrier Dynamics in Porphyrin Nanorings by Optically Active Templates.

Understanding the dynamics of photogenerated charge carriers is essential for enhancing the performance of solar and optoelectronic devices. Using atomistic quantum dynamics simulations, we demonstrate that a short π-conjugated optically active template can be used to control hot carrier relaxation, charge carrier separation, and carrier recombination in light-harvesting porphyrin nanorings. Relaxation of hot holes is slowed by 60% with an optically active template compared to that with an analogous optically inactive template.

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 (Cu(HFcHBC)) based on a fluorinated core-twisted contorted hexahydroxy-hexa-cata-hexabenzocoronene (HFcHBC) ligand.

Plasmonic Resonant Intercluster Coulombic Decay.

Light-induced energy confinement in nanoclusters via plasmon excitations influences applications in nanophotonics, photocatalysis, and the design of controlled slow electron sources. The resonant decay of these excitations through the cluster's ionization continuum provides a unique probe of the collective electronic behavior. However, the transfer of a part of this decay amplitude to the continuum of a second conjugated cluster may offer control and efficacy in sharing the energy nonlocally to instigate remote collective events.

Ultrafast Laser Control of Antiferromagnetic-Ferrimagnetic Switching in Two-Dimensional Ferromagnetic Semiconductor Heterostructures.

Realizing ultrafast control of magnetization switching is of crucial importance for information processing and recording technology. Here, we explore the laser-induced spin electron excitation and relaxation dynamics processes of CrCl/CrBr heterostructures with antiparallel (AP) and parallel (P) systems. Although an ultrafast demagnetization of CrCl and CrBr layers occurs in both AP and P systems, the overall magnetic order of the heterostructure remains unchanged due to the laser-induced equivalent interlayer spin electron excitation.

Boosting the photoelectrochemical performance of bismuth vanadate photoanode through homojunction construction.

The photoelectrochemical (PEC) performance of bismuth vanadate (BiVO) suffers from sluggish charge mobility and substantial charge recombination losses due to its intrinsic defect. To rectify the problem, we developed a novel approach to prepare an n-n type II BVO-BVO homojunction with staggered band alignment. This architecture involves a built-in electric field that facilitating the electron-hole separation at the BVO/BVO interface.

Molecular dynamics study of plasmon-mediated chemical transformations.

Heterogeneous catalysis of adsorbates on metallic surfaces mediated by plasmons has potential high photoelectric conversion efficiency and controllable reaction selectivity. Theoretical modeling of dynamical reaction processes enables in-depth analyses complementing experimental investigations. Especially for plasmon-mediated chemical transformations, light absorption, photoelectric conversion, electron-electron scattering, and electron-phonon coupling occur simultaneously on different timescales, making it very challenging to delineate the complex interplay of different factors.

Insight into the Molecular Mechanism for Enhanced Longevity of Supramolecular Vesicular Photocatalysts.

Supramolecular self-assembly is a promising strategy for stabilizing the photo-sensitive components in photocatalysis. However, the underlying correlation between the enhanced photostability and supramolecular structure at the molecular level has not yet been fully understood. Herein, we develop a biomimetic vesicular membrane-based polyporphyrin photocatalyst exhibiting excellent photocatalytic stability with at least activity time of 240 h in hydrogen generation.

Predicting the Lattice Thermal Conductivity in Nitride Perovskite LaWN from ab initio Lattice Dynamics.

Using a density functional theory-based thermal transport model, which includes the effects of temperature (T)-dependent potential energy surface, lattice thermal expansion, force constant renormalization, and higher-order quartic phonon scattering processes, it is found that the recently synthesized nitride perovskite LaWN displays strong anharmonic lattice dynamics manifested into a low lattice thermal conductivity (κ ) and a non-standard κ ∝T dependence. At high T, the departure from the standard κ ∝T law originates in the dual particle-wave behavior of the heat carrying phonons, which includes vibrations tied to the N atoms. While the room temperature κ =2.

Carrier Relaxation and Multiplication in Bi Doped Graphene.

By introducing different contents of Bi adatoms to the surface of monolayer graphene, the carrier concentration and their dynamics have been effectively modulated as probed directly by the time- and angle-resolved photoemission spectroscopy technique. The Bi adatoms are found to assist acoustic phonon scattering events mediated by supercollisions as the disorder effectively relaxes the momentum conservation constraint. A reduced carrier multiplication has been observed, which is related to the shrinking Fermi sea for scattering, as confirmed by time-dependent density functional theory simulation.

Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics.

Hot carriers generated from the decay of plasmon excitation can be harvested to drive a wide range of physical or chemical processes. However, their generation efficiency is limited by the concomitant phonon-induced relaxation processes by which the energy in excited carriers is transformed into heat. However, simulations of dynamics of nanoscale clusters are challenging due to the computational complexity involved.

Intrinsic Ferroelectric Quantum Spin Hall Insulator in Monolayer NaBi 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.

Obtaining Electronic Properties of Molecules through Combining Density Functional Tight Binding with Machine Learning.

We have introduced a machine learning workflow that allows for optimizing electronic properties in the density functional tight binding method (DFTB). The workflow allows for the optimization of electronic properties by generating two-center integrals, either by training basis function parameters directly or by training a spline model for the diatomic integrals, which are then used to build the Hamiltonian and the overlap matrices. Using our workflow, we have managed to obtain improved electronic properties, such as charge distributions, dipole moments, and approximated polarizabilities.

DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science.

In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022.

Surface-Mounted Dipolar Molecular Rotors Driven by External Electric Field, As Revealed by Torque Analyses.

Driven by a high-speed rotating electric field (-field), molecular motors with polar groups may perform a unidirectional, repetitive, and GHz frequency rotation and thus offer potential applications as nanostirrers. To drive the unidirectional rotation of molecular motors, it is crucial to consider factors of internal charge flow, thermal noise, molecular flexibility, and so forth before selecting an appropriate frequency of a rotating -field. Herein, we studied two surface-mounted dipolar rotors of a "caltrop-like" molecule and a "sandwich" molecule by using quantum-mechanical computations in combination with torque analyses.

Charge Transfer Doping of Carbon Nitride Films through Noncovalent Iodination for Enhanced Photoelectrochemical Performance: Combined Experimental and Computational Insights.

To improve the photoelectrochemical (PEC) performance of photocatalysts, the doping strategy through covalent functionalization is often adopted to adjust material electronic structures. By contrast, this work demonstrates that the noncovalent interaction in the case of iodinated graphitic carbon nitride (g-CN) film can also enhance the PEC performance. Through a facile synthesis method of rapid thermal vapor condensation (RTVC), the prepared iodinated g-CN film shows a significantly improved photocurrent density (38.

Control of Hot Carrier Cooling in Lead Halide Perovskites by Point Defects.

Hot carriers (HCs) in lead halide perovskites are prone to rapidly relax at the band edge and waste plentiful photon energy, severely limiting their conversion efficiency as HC photovoltaic devices. Here, the HC cooling dynamics of MAPbI perovskite with common vacancy point defects (e.g.

Carrier Multiplication in Transition Metal Dichalcogenides Beyond Threshold Limit.

Carrier multiplication (CM), multiexciton generation by absorbing a single photon, enables disruptive improvements in photovoltaic conversion efficiency. However, energy conservation constrains the threshold energy to at least twice bandgap (2 ). Here, a below threshold limit CM in monolayer transition metal dichalcogenides (TMDCs) is reported.

Nonadiabatic molecular dynamics simulations based on time-dependent density functional tight-binding method.

Nonadiabatic excited state molecular dynamics underpin many photophysical and photochemical phenomena, such as exciton dynamics, and charge separation and transport. In this work, we present an efficient nonadiabatic molecular dynamics (NAMD) simulation method based on time-dependent density functional tight-binding (TDDFTB) theory. Specifically, the adiabatic electronic structure, an essential NAMD input, is described at the TDDFTB level.

Four-phonon and electron-phonon scattering effects on thermal properties in two-dimensional 2H-TaS.

Thermal transport characteristics of monolayer trigonal prismatic tantalum disulfide (2H-TaS) are investigated using first-principles calculations combined with the Boltzmann transport equation. Due to a large acoustic-optical phonon gap of 1.85 THz, the four-phonon (4ph) scattering significantly reduces the room-temperature phononic thermal conductivity ().

WS-Flake-Sandwiched, Au-Nanodisk-Enabled High-Quality Fabry-Pérot Nanoresonators for Photoluminescence Modulation.

The increasing demand for compact and high-performance photonic devices drives the development of optical resonators with nanoscale sizes and ultrahigh quality factors. Fabry-Pérot (FP) resonators, the most widely employed optical resonators, can support ultrahigh quality factors in the simple structure, which is particularly attractive for applications in lasers, filters, and ultrasensitive sensors. However, the construction of FP resonators with both nanoscale sizes and high quality factors has still faced challenges.

Heterogeneous-Interface-Enhanced Adsorption of Organic and Hydroxyl for Biomass Electrooxidation.

Electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) provides an efficient way to obtain high-value-added biomass-derived chemicals. Compared with other transition metal oxides, CuO exhibits poor oxygen evolution reaction performance, leading to high Faraday efficiency for HMF oxidation. However, the weak adsorption and activation ability of CuO to OH species restricts its further development.

First-Principles Nonequilibrium Green's Function Approach to Energy Conversion in Nanoscale Optoelectronics.

Understanding photon-electron conversion on the nanoscale is essential for future innovations in nano-optoelectronics. In this article, based on nonequilibrium Green's function (NEGF) formalism, we develop a quantum-mechanical method for modeling energy conversion in nanoscale optoelectronic devices. The method allows us to study photoinduced charge transport and electroluminescence processes in realistic devices.