A direct diabatic states construction method with consistent orbitals for valence and Rydberg states.

This work presents a novel methodology termed Direct Diabatic States Construction (DDSC), which integrates fragment wavefunctions into an anti-symmetric wavefunction for the entire system. Using fragment-localized state-consistent molecular orbitals, this approach enables direct construction of all diabatic states at the same root. Each diabatic state is formed as a linear combination of a set of diabatic configurations.

Triple-T Method for Modeling Plasma-Assisted Ignition with Rich Vibrationally Excited States.

Vibrationally excited species play an important role in elevating the gas temperature and reaction rates in fuel-plasma reaction systems. Classical two-temperature models coupled with the well-known Fridman-Macheret α-model have been validated and widely used to describe the plasma and fuel systems. However, the Fridman-Macheret α-model strictly requires the information on elementary reaction rates.

Many-Body Expansion-Based Quantum Mechanical Force Field for Cyclotrimethylene Trinitramine under High Pressure.

RDX undergoes pressures of approximately 30-50 GPa during detonation, leading to significant changes in intermolecular interactions. Accurately describing these interactions is crucial for understanding the energy transfer in the detonation process. To address this, this work introduces a many-body expansion-based quantum mechanical force field (MB-QMFF) to accurately describe RDX's intermolecular interactions under high pressures.

Importance of Spin Channels from Radical-Radical Reactions in Hydrogen-Oxygen Combustion Mechanisms at High Temperatures.

Radical-radical reactions can generate two channels with high and low spins. In this work, ten radical-radical reactions with different spin channels and four radical-molecule reactions in hydrogen-oxygen combustion were systematically investigated from a theoretical perspective. The potential energy surface (PES) of radical-radical reactions reveals that the high- and low-spin states of the reactant are energetically degenerate and the two channels are energetically feasible.

Diradical-Based Strategy in Designing Narrowband Thermally Activated Delayed Fluorescence Molecules with Tunable Emission Wavelengths.

In the design of thermally activated delayed fluorescence (TADF) materials, narrow-band emission is of particular importance for the development of organic light-emitting diodes (OLEDs). In this work, we proposed a new strategy for designing TADF molecules utilizing degenerate nonbonding (NB) orbitals of diradical parent molecules, and these designed molecules are termed NB-TADF molecules. Based on this strategy, a series of NB-TADF molecules is finely designed and systematically studied by theoretical calculations.

Ultrafast vibrational energy redistribution in cyclotrimethylene trinitramine (RDX).

The microscopic mechanism of the energy transfer in cyclotrimethylene trinitramine (RDX) is of particular importance for the study of the energy release process in high-energy materials. In this work, an effective vibrational Hamiltonian based on normal modes (NMs) has been introduced to study the energy transfer process of RDX. The results suggest that the energy redistribution in RDX can be characterized as an ultrafast process with a time scale of 25 fs, during which the energy can be rapidly localized to the -NNO2 twisting mode (vNNO2), the N-N stretching mode (vN-N), and the C-H stretching mode (vC-H).

Energy transfer from two luteins to chlorophylls in light-harvesting complex II study by using exciton models with phase correction.

In light-harvesting complex II of plants, the two lutein pigments (LUT1 and LUT2) are always paired and an energy transfer pathway between them is believed to exist. However, it remains unclear whether this pathway is essential for the energy transfer between carotenoids and chlorophylls. In this work, we performed hybrid quantum mechanics/molecular mechanics simulations with Frenkel exciton models to investigate this energy transfer.

Enabling Carbonized Polymer Dots with Color-tunable Time-dependent Room Temperature Phosphorescence through Confining Carboxyl Dimer Association.

Developing a facile strategy to realize fine-tuning of phosphorescence color in time-dependent room temperature phosphorescence (RTP) materials is essential but both theoretically and practically rarely exploited. Through simultaneously confining carboxyl dimer association and isolated carboxyl into the particle via a simple hydrothermal treatment of polyacrylic acid, a dual-peak emission of red phosphorescence (645 nm) and green phosphorescence (550 nm) was observed from carbonized polymer dots (CPDs). The ratio of the two luminescent species can be well regulated by hydrochloric acid inhibiting the dissociation of carboxyl to promote hydrogen bond.

Mesomerism induced temperature-dependent multicomponent phosphorescence emissions in ClBDBT.

Quantum mechanics/molecular mechanics (QM/MM) and molecular dynamics (MD) methods were applied to systematically investigate the temperature-dependent phosphorescence emission of dibenzo[,]thiophen-2-yl(4-chlorophenyl)methanone (ClBDBT) and its derivatives. The calculated temperature-dependent spectra on the lowest triplet state (T) are in good agreement with the experimental observations, which means that the two-component white light emission should stem from the T state. The further MD simulations demonstrate the existence of two mesomerism structures at room temperature which can emit two lights simultaneously.

Intermolecular resonance energy transfer between two lutein pigments in light-harvesting complex II studied by frenkel exciton models.

The energy transfer pathways in light-harvesting complex II are complicated and the discovery of the energy transfer between the two luteins revealed an unelucidated important role of carotenoids in the energy flow. This energy transfer between the two S states of luteins was for the first time investigated using Frenkel exciton models, using a hybrid scheme of molecular mechanics and quantum mechanics. The results show the energy flow between the two luteins under the Förster resonance energy transfer mechanism.

Controlling the repair mechanisms of oxetanes through functional group substitution.

Intersystem crossing (ISC) plays a key role in the photolysis processes of oxetanes formed by benzophenone (BP)-like and thymine structures. In this work, we systematically explored the photophysical processes of oxetanes and ring-splitting products and investigated the effect of substituents on the repair mechanisms of oxetanes. The regioselectivity of oxetanes (head-to-head, HH and head-to-tail, HT) and the electron-donating and electron-withdrawing substituents, including CH, OCH and NO, were considered.

Rational adjustment to interfacial interaction with carbonized polymer dots enabling efficient large-area perovskite light-emitting diodes.

Film uniformity of solution-processed layers is the cornerstone of large-area perovskite light-emitting diodes, which is often determined by the 'coffee-ring effect'. Here we demonstrate a second factor that cannot be ignored is the solid-liquid interface interaction between substrate and precursor and can be optimized to eliminate rings. A perovskite film with rings can be formed when cations dominate the solid-liquid interface interaction; whereas smooth and homogeneous perovskite emitting layers are generated when anions and anion groups dominate the interaction.

Benchmark Study on Phosphorescence Energies of Anthraquinone Compounds: Comparison between TDDFT and UDFT.

Phosphorescent material is widely used in light-emitting devices and in the monitoring of cell phenomena. Anthraquinone compounds (AQs), as important phosphorescent materials, have potential applications as emitters for highly efficient organic light-emitting diodes (OLEDs). Therefore, the accurate calculation of the phosphorescence energy of anthraquinone compounds is particularly important.

A theoretical roadmap for the best oxygen reduction activity in two-dimensional transition metal tellurides.

Developing highly active and cost-effective electrocatalysts to replace Pt-based catalysts for the sluggish oxygen reduction reaction (ORR) is a major challenge in the commercialization of fuel cells. Although two-dimensional (2D) transition-metal tellurides have recently been proposed as alternative low-cost ORR catalysts, a fundamental study on the origin of the activity is required to further optimize their composition and performance. Herein, we investigated the electronic properties and ORR catalytic performances of a series of exfoliable 2D transition-metal tellurides to uncover the underlying mechanisms by means of density functional theory simulations.

Dearomatization of Benzenoid Arenes Triggered by Triplet Excited State Intramolecular Proton Transfer.

The detailed mechanism of photoinduced dearomatization of benzenoid arenes is investigated using both the high-level method and density functional theory. The results suggest that the optically allowed singlet excited state (S) can quickly decay to the lowest triplet excited state (T) through a barrierless internal conversion and intersystem crossing. Importantly, we find a triplet excited state intramolecular proton transfer (T-ESIPT) pathway to produce a diradical triplet intermediate (M), which can trigger the subsequent [4 + 2] dearomatization reaction.

Minimal Active Space for Diradicals Using Multistate Density Functional Theory.

This work explores the electronic structure as well as the reactivity of singlet diradicals, making use of multistate density functional theory (MSDFT). In particular, we show that a minimal active space of two electrons in two orbitals is adequate to treat the relative energies of the singlet and triplet adiabatic ground state as well as the first singlet excited state in many cases. This is plausible because dynamic correlation is included in the first place in the optimization of orbitals in each determinant state via block-localized Kohn-Sham density functional theory.

Generation of singlet oxygen catalyzed by the room-temperature-stable anthraquinone anion radical.

The chemical nature and the catalytic selectivity of the complex of anthraquinone and potassium -butoxide, AQ-KOBu, in generating singlet oxygen (O) have been studied using a high-level method and density functional theory (DFT). The results suggest that the stable catalytic center of the AQ anion radical (semiquinone, [AQ˙]) can be produced at room temperature, which is due to the strong delocalization characteristics of electrons in potassium atoms. Two experimentally observed complexes, the ground state AQ-KOBu, , C, and the photoexcited AQ-KOBu, , C, can be distinguished the two different electronic states (π-type and σ-type) of the -butoxide group.

Top-Down Rational Engineering of Heteroatom-Doped Graphene Quantum Dots for Laser Desorption/Ionization Mass Spectrometry Detection and Imaging of Small Biomolecules.

Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) is widely applied in mapping macrobiomolecules in tissues, but it is still limited in profiling low-molecular-weight (MW) compounds (typically metabolites) due to ion interference and suppression by organic matrices. Here, we present a versatile "top-down" strategy for rational engineering of carbon material-based matrices, by which heteroatom-doped graphene quantum dots (HGQDs) were manufactured for LDI MS detection and imaging of small biomolecules. The HGQDs derived from parent materials inherited the π-conjugated networks and doping sites for promoting energy transfer and negative ion generation, while their extremely small size guaranteed the matrix uniformity and signal reproducibility in LDI MSI.

Community Reaction Network Reduction for Constructing a Coarse-Grained Representation of Combustion Reaction Mechanisms.

A community-reaction network reduction (CNR) approach is presented for mechanism reduction on the basis of a network-based community detection technique, a concept related to pre-equilibrium in chemical kinetics. In this method, the detailed combustion mechanism is first transformed into a weighted network, in which communities of species that have dense inner connections under the critical ignition conditions are identified. By analyzing the community partitions in different regions, we determine the effective functional groups and driving processes.

Lack of the ESIPT band of aromatic -aminoaldehyde derivatives triggered by N-H vibration.

The excited state intramolecular proton transfer (ESIPT) reactions and the fluorescence emission spectra of -aminoaldehyde and -aminoketone derivatives were systematically studied with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The results suggest that the ESIPT process can be characterized as an ultra-fast process and that N-H vibration plays an important role in fluorescence emissions. The minimum energy pathways (MEP) on the excited states along the proton transfer coordinates (N-H vibration) were constructed for both -aminoaldehyde and -aminoketone derivatives, respectively, which showed a small barrier between the normal and tautomer (ESIPT) structures.

A new permutation-symmetry-adapted machine learning diabatization procedure and its application in MgH system.

This work introduces a new permutation-symmetry-adapted machine learning diabatization procedure, termed the diabatization by equivariant neural network (DENN). In this approach, the permutation symmetric and anti-symmetric elements in diabatic potential energy metrics (DPEMs) were simultaneously simulated by the equivariant neural network. The diabatization by deep neural network scheme was adopted for machine learning diabatization, and non-zero diabatic coupling was included to increase accuracy in the near degenerate region.

Theoretical Study of a Two-Photon Fluorescent Probe Based on Nile Red Derivatives with Controllable Fluorescence Wavelength and Water Solubility.

Hypochloric acid (HOCl) plays a vital role in the natural defense system, but abnormal levels of it can cause cell damage, accelerated human aging, and various diseases. It is of great significance to develop new probes for detecting HOCl in biosystems nondestructively and noninvasively. The purpose of this work is to explore new chemical modification strategies of two-photon excitation fluorescence (TPEF) probes to improve the poor water solubility and low efficiency in imaging applications.

Impact of Δ on Delayed Fluorescence Rate, Lifetime, and Intensity Ratio of Tetrahedral Cu(I) Complexes: Theoretical Simulation in Solution and Solid Phases.

Profound understanding of the luminescence mechanism and structure-property relationship is vital for Cu(I) thermally activated delayed fluorescence (TADF) emitters. Herein, we theoretically simulated luminescent behavior in both solution and solid phases for two Cu(I) complexes and found the following: (i) The strengthened spin-orbit coupling (SOC) effect by more d orbital contributions and well-restricted structural distortion via remarkable intramolecular interaction in [Cu(dmp)(POP)] enable the emission at room temperature to be a mixture of direct phosphorescence (10%) and TADF (90%). (ii) Benefiting from enhanced steric hindrance and the electron-donating ability of the paracyclophane group, the narrowed S-T energy separation (Δ) in [Cu(dmp)(phanephos)] accelerates the reverse intersystem crossing, promoting the TADF rate (1.