Prediction of photodynamics of 200 nm excited cyclobutanone with linear response electronic structure and ab initio multiple spawning.

Simulations of photochemical reaction dynamics have been a challenge to the theoretical chemistry community for some time. In an effort to determine the predictive character of current approaches, we predict the results of an upcoming ultrafast diffraction experiment on the photodynamics of cyclobutanone after excitation to the lowest lying Rydberg state (S2). A picosecond of nonadiabatic dynamics is described with ab initio multiple spawning. We use both time dependent density functional theory (TDDFT) and equation-of-motion coupled cluster singles and doubles (EOM-CCSD) theory for the underlying electronic structure theory. We find that the lifetime of the S2 state is more than a picosecond (with both TDDFT and EOM-CCSD). The predicted ultrafast electron diffraction spectrum exhibits numerous structural features, but weak time dependence over the course of the simulations.

Existence and uniqueness of well-posed fractional boundary value problem.

In this paper, the existence and uniqueness of solution for a fractional differential model involving well-posed boundary conditions and implicit fractional differential equation is considered. The desired goals are achieved by using Banach contraction principle and Scheafer's fixed point theorem. To show the results applicability some examples are presented. The basic mathematical concept of well-posed fractional boundary value issues is investigated in this study. It dives into the existence and uniqueness of these difficulties, offering light on the conditions that allow for both practical and singular solutions. This study contributes to a better knowledge of fractional calculus and its applications in a variety of scientific and technical areas, giving significant insights for both scholars and practitioners.

Minimizing non-radiative decay in molecular aggregates through control of excitonic coupling.

The widely known "Energy Gap Law" (EGL) predicts a monotonically exponential increase in the non-radiative decay rate (knr) as the energy gap narrows, which hinders the development of near-infrared (NIR) emissive molecular materials. Recently, several experiments proposed that the exciton delocalization in molecular aggregates could counteract EGL to facilitate NIR emission. In this work, the nearly exact time-dependent density matrix renormalization group (TD-DMRG) method is developed to evaluate the non-radiative decay rate for exciton-phonon coupled molecular aggregates. Systematical numerical simulations show, by increasing the excitonic coupling, knr will first decrease, then reach a minimum, and finally start to increase to follow EGL, which is an overall result of two opposite effects of a smaller energy gap and a smaller effective electron-phonon coupling. This anomalous non-monotonic behavior is found robust in a number of models, including dimer, one-dimensional chain, and two-dimensional square lattice. The optimal excitonic coupling strength that gives the minimum knr is about half of the monomer reorganization energy and is also influenced by system size, dimensionality, and temperature.

TeraChem protocol buffers (TCPB): Accelerating QM and QM/MM simulations with a client-server model.

The routine use of electronic structures in many chemical simulation applications calls for efficient and easy ways to access electronic structure programs. We describe how the graphics processing unit (GPU) accelerated electronic structure program TeraChem can be set up as an electronic structure server, to be easily accessed by third-party client programs. We exploit Google's protocol buffer framework for data serialization and communication. The client interface, called TeraChem protocol buffers (TCPB), has been designed for ease of use and compatibility with multiple programming languages, such as C++, Fortran, and Python. To demonstrate the ease of coupling third-party programs with electronic structures using TCPB, we have incorporated the TCPB client into Amber for quantum mechanics/molecular mechanics (QM/MM) simulations. The TCPB interface saves time with GPU initialization and I/O operations, achieving a speedup of more than 2× compared to a prior file-based implementation for a QM region with ∼250 basis functions. We demonstrate the practical application of TCPB by computing the free energy profile of p-hydroxybenzylidene-2,3-dimethylimidazolinone (p-HBDI-)-a model chromophore in green fluorescent proteins-on the first excited singlet state using Hamiltonian replica exchange for enhanced sampling. All calculations in this work have been performed with the non-commercial freely-available version of TeraChem, which is sufficient for many QM region sizes in common use.

The Variance of Photophysical Properties of Tetraphenylethene and Its Derivatives during Their Transitions from Dissolved States to Solid States.

The study of aggregation-induced emission luminogens (AIEgens) shows promising perspectives explored in lighting, optical sensors, and biological therapies. Due to their unique feature of intense emissions in aggregated solid states, it smoothly circumvents the weaknesses in fluorescent dyes, which include aggregation-caused quenching of emission and poor photobleaching character. However, our present knowledge of the AIE phenomena still cannot comprehensively explain the mechanism behind the substantially enhanced emission in their aggregated solid states. Herein, to systematically study the mechanism, the typical AIEgens tetraphenylethene (TPE) was chosen, to elucidate its photophysical properties, the TPE in THF/H2O binary solvents, TPE in THF solvents depending on concentration, and the following direct conversion from a dissolved state to a precipitated solid state were analyzed. Moreover, the TPE derivatives were also investigated to supply more evidence to better decipher the generally optical behaviors of TPE and its derivatives. For instance, the TPE derivative was homogeneously dispersed into tetraethyl orthosilicate to monitor the variance of photophysical properties during sol-gel processing. Consequently, TPE and its derivatives are hypothesized to abide by the anti-Kasha rule in dissolved states. In addition, the factors primarily influencing the nonlinear emission shifting of TPE and its derivatives are also discussed.

Hybrid Quantum-Classical Boson Sampling Algorithm for Molecular Vibrationally Resolved Electronic Spectroscopy with Duschinsky Rotation and Anharmonicity.

Using a photonic quantum computer for boson sampling has demonstrated a tremendous advantage over classical supercomputers. It is highly desirable to develop boson sampling algorithms for realistic scientific problems. In this work, we propose a hybrid quantum-classical sampling (HQCS) algorithm to calculate the optical spectrum for complex molecules considering Duschinsky rotation effects and anharmonicity. The classical sum-over-states method for this problem has a computational complexity that exponentially increases with system size. The HQCS algorithm creates an intermediate harmonic potential energy surface (PES) to bridge the initial and final PESs. The magnitude and sign of the overlap between the initial and the intermediate state are estimated by boson sampling and classical algorithms, respectively. The overlap between the intermediate and the final state is efficiently evaluated by classical algorithms. The feasibility of HQCS is demonstrated in calculations of the emission spectrum of a Morse model as well as the pyridine molecule.

InteraChem: Exploring Excited States in Virtual Reality with Ab Initio Interactive Molecular Dynamics.

InteraChem is an ab initio interactive molecular dynamics (AI-IMD) visualizer that leverages recent advances in virtual reality hardware and software, as well as the graphical processing unit (GPU)-accelerated TeraChem electronic structure package, in order to render quantum chemistry in real time. We introduce the exploration of electronically excited states via AI-IMD using the floating occupation molecular orbital-complete active space configuration interaction method. The optimization tools in InteraChem enable identification of excited state minima as well as minimum energy conical intersections for further characterization of excited state chemistry in small- to medium-sized systems. We demonstrate that finite-temperature Hartree-Fock theory is an efficient method to perform ground state AI-IMD. InteraChem allows users to track electronic properties such as molecular orbitals and bond order in real time, resulting in an interactive visualization tool that aids in the interpretation of excited state chemistry data and makes quantum chemistry more accessible for both research and educational purposes.

Transcriptome and Metabolome Analysis Revealed the Freezing Resistance Mechanism in 60-Year-Old Overwintering Camellia sinensis.

Freezing stress in winter is the biggest obstacle to the survival of C. sinensis in mid-latitude and high-latitude areas, which has a great impact on the yield, quality, and even life of C. sinensis every year. In this study, transcriptome and metabolome were used to clarify the freezing resistance mechanism of 60-year-old natural overwintering C. sinensis under freezing stress. Next, 3880 DEGs and 353 DAMs were obtained. The enrichment analysis showed that pathways of MAPK and ABA played a key role in the signal transduction of freezing stress, and Pyr/PYL-PP2C-SnRK2 in the ABA pathway promoted stomatal closure. Then, the water holding capacity and the freezing resistance of C. sinensis were improved. The pathway analysis showed that DEGs and DAMs were significantly enriched and up-regulated in the three-related pathways of phenylpropanoid biosynthesis, flavone and flavonol biosynthesis, and flavonoid biosynthesis. In addition, the carbohydrate and fatty acid synthesis pathways also had a significant enrichment, and the synthesis of these substances facilitated the freezing resistance. These results are of great significance to elucidate the freezing resistance mechanism and the freezing resistance breeding of C. sinensis.

Evaluating the anharmonicity contributions to the molecular excited state internal conversion rates with finite temperature TD-DMRG.

In this work, we propose a new method to calculate molecular nonradiative electronic relaxation rates based on the numerically exact time-dependent density matrix renormalization group theory. This method could go beyond the existing frameworks under the harmonic approximation (HA) of the potential energy surface (PES) so that the anharmonic effect could be considered, which is of vital importance when the electronic energy gap is much larger than the vibrational frequency. We calculate the internal conversion (IC) rates in a two-mode model with Morse potential to investigate the validity of HA. We find that HA is unsatisfactory unless only the lowest several vibrational states of the lower electronic state are involved in the transition process when the adiabatic excitation energy is relatively low. As the excitation energy increases, HA first underestimates and then overestimates the IC rates when the excited state PES shifts toward the dissociative side of the ground state PES. On the contrary, HA slightly overestimates the IC rates when the excited state PES shifts toward the repulsive side. In both cases, a higher temperature enlarges the error of HA. As a real example to demonstrate the effectiveness and scalability of the method, we calculate the IC rates of azulene from S1 to S0 on the ab initio anharmonic PES approximated by the one-mode representation. The calculated IC rates of azulene under HA are consistent with the analytically exact results. The rates on the anharmonic PES are 30%-40% higher than the rates under HA.

Crystalline carbon modified hierarchical porous iron and nitrogen co-doped carbon for efficient electrocatalytic oxygen reduction.

Hierarchical porous iron and nitrogen co-doped carbon (Fe-N/C) materials have been considered as an appealing non-noble metal-based catalyst in oxygen reduction reactions (ORR). However, the conductivity loss caused by the scattering of electrons on pores and defects markedly limits their catalytic activity, which attracted seldom attention in this area. Herein, a novel crystalline carbon modified hierarchical porous Fe-N/C electrocatalyst with enhanced electronic conductivity is designed and prepared via a two-step calcination-catalysis process. The resistivity of hierarchical porous Fe-N/C is decreased from 2.123 Ω cm to 0.479 Ω cm after crystalline carbon introduction. The electrocatalyst annealed at 800 °C (Fe-N/C-800) exhibits a superior activity with the half-wave potential (E1/2) of 0.89 V, which outperforms the commercial carbon-supported platinum (Pt/C) catalyst (0.85 V). The strategy of crystalline carbon modification provides a fresh approach to improve the electronic conductivity of porous carbon-based materials.

Intrinsic hydroquinone-functionalized aggregation-induced emission core shows redox and pH sensitivity.

Aggregation-induced emission (AIE) fluorophores exhibit strong fluorescence in an aggregated state but emit no or weak fluorescence in dilute solutions. This emerging class of AIE optical materials comprise a variety of functionalities. Here an AIE luminescence core, 1-hydroquinol-1,2,2-triphenylethene (HQTPE), has been designed and synthesized. This AIE core is simple but is fundamentally important to chemistry because of its intrinsic redox and pH activities. The incorporation of hydroquinone (HQ) moiety into a common AIE core tetraphenylethene (TPE) yields HQTPE with unique fluorescent properties like nonlinear self-quenching over most other AIE-active fluorophores (AIEgens) so far reported. There are differences of photochemical properties between HQTPE, 1-benzoquinol-1,2,2-triphenylethene (QTPE, the oxidized counterpart) and its anions. Interestingly, as the solution concentration is increased, AIEgen HQTPE shows stronger fluorescence but QTPE exhibits rapid quenching of fluorescence in a nonlinear fashion, which are in agreement with theoretical studies. The fluorescence of HQTPE is also highly dependent on the pH value of media. We have further explored HQTPE as an ultrasensitive redox probe and efficient deoxidizer, which could lead to potential applications in health care, food security, environmental monitoring, optic and electronic devices.

Performance of Coupled-Cluster Singles and Doubles on Modern Stream Processing Architectures.

We develop a new implementation of coupled-cluster singles and doubles (CCSD) optimized for the most recent graphical processing unit (GPU) hardware. We find that a single node with 8 NVIDIA V100 GPUs is capable of performing CCSD computations on roughly 100 atoms and 1300 basis functions in less than 1 day. Comparisons against massively parallel implementations of CCSD suggest that more than 64 CPU-based nodes (each with 16 cores) are required to match this performance.

Leaving Group Assisted Strategy for Photoinduced Fluoroalkylations Using N-Hydroxybenzimidoyl Chloride Esters.

Redox-active esters (RAEs) as alkyl radical precursors have been extensively developed for C-C bond formations. However, the analogous transformations of fluoroalkyl radicals from the corresponding acid or ester precursors remain challenging because of the high oxidation potential of the fluoroalkyl carboxylate anions. The newly developed N-hydroxybenzimidoylchloride (NHBC) ester provides a general leaving group assisted strategy to generate a portfolio of fluoroalkyl radicals, and can be successfully applied in photoinduced decarboxylative hydrofluoroalkylation and heteroarylation of unactivated olefins. In addition, DFT calculations revealed that the NHBC ester proceeds by the fluorocarbon radical pathway, whereas other well-known RAEs proceed by the nitrogen radical pathway.