Search

Common one-electron reduced density matrix (1-RDM) functionals that depend on Coulomb and exchange-only integrals tend to underestimate dynamic correlation, preventing reduced density matrix functional theory (RDMFT) from achieving comparable accuracy to density functional theory in main-group thermochemistry and thermochemical kinetics. The recently developed ωP22 functional introduces a semi-local density functional to screen the erroneous short-range portion of 1-RDM functionals without double-counting correlation, potentially providing a better treatment of dynamic correlation around equilibrium geometries. Herein, we systematically evaluate the performance of this functional model, which consists of two parameters, on main-group thermochemistry, thermochemical kinetics, nonbonded interactions, and more. Tests on atomization energies, vibrational frequencies, and reaction barriers reveal that the ωP22 functional model can reliably predict properties at equilibrium and slightly away from equilibrium geometries. In particular, it outperforms commonly used density functionals in the prediction of reaction barriers, nonbonded interactions, and singlet diradicals, thus enhancing the predictive power of RDMFT for routine calculations of thermochemistry and thermochemical kinetics around equilibrium geometries. Further development is needed in the future to refine short- and long-range approximations in the functional model in order to achieve an excellent description of properties both near and far from equilibrium geometries. [ABSTRACT FROM AUTHOR]

Recently, we developed a low-scaling Multi-Layer Energy-Based Fragment (MLEBF) method for accurate excited-state calculations and nonadiabatic dynamics simulations of nonbonded fragment systems. In this work, we extend the MLEBF method to treat covalently bonded fragment ones. The main idea is cutting a target system into many fragments according to chemical properties. Fragments with dangling bonds are first saturated by chemical groups; then, saturated fragments, together with the original fragments without dangling bonds, are grouped into different layers. The accurate total energy expression is formulated with the many-body energy expansion theory, in combination with the inclusion–exclusion principle that is used to delete the contribution of chemical groups introduced to saturate dangling bonds. Specifically, in a two-layer MLEBF model, the photochemically active and inert layers are calculated with high-level and efficient electronic structure methods, respectively. Intralayer and interlayer energies can be truncated at the two- or three-body interaction level. Subsequently, through several systems, including neutral and charged covalently bonded fragment systems, we demonstrate that MLEBF can provide accurate ground- and excited-state energies and gradients. Finally, we realize the structure, conical intersection, and path optimizations by combining our MLEBF program with commercial and free packages, e.g., ASE and SciPy. These developments make MLEBF a practical and reliable tool for studying complex photochemical and photophysical processes of large nonbonded and bonded fragment systems. [ABSTRACT FROM AUTHOR]

Nonlinear optical (NLO) materials are of great importance in modern optics and industry because of their intrinsic capability of wavelength conversion. Bandgap is a key property of NLO crystals. In recent years, machine learning (ML) has become a powerful tool to predict the bandgaps of compounds before synthesis. However, the shortage of available experimental data of NLO crystals poses a significant challenge for the exploration of new NLO materials using ML. In this work, we proposed a new multi-fidelity ML approach based on the multilevel descriptors developed by us (Z.-Y. Zhang, X. Liu, L. Shen, L. Chen and W.-H. Fang, J. Phys. Chem. C, 2021, 125, 25175–25188) and the gradient boosting regression tree algorithm. The calculated and experimental bandgaps of NLO crystals were collected as the low- and high-fidelity labels, respectively. The experimental values were predicted based on chemical compositions of crystals without prior knowledge about crystal structures. The multi-fidelity ML model overcame the performance of single-fidelity predictor. Furthermore, it was observed that less accurate predictions on the low-fidelity label may result in more accurate prediction on the high-fidelity label, at least in the present case. Using the multi-fidelity ML model with the best performance in this work, the mean absolute error on the test set of experimental bandgaps was 0.293 eV, which is smaller than that using the single-fidelity model (0.355 eV). It is far from perfect but accurate enough as an effective computational tool in the first step to discover novel NLO materials. [ABSTRACT FROM AUTHOR]

Molecular ultralong room‐temperature phosphorescence (RTP), exhibiting multiple stimuli‐responsive characteristics, has garnered considerable attention due to its potential applications in light‐emitting devices, sensors, and information safety. This work proposes the utilization of photochemical cascade processes (PCCPs) in molecular crystals to design a stepwise smart RTP switch. By harnessing the sequential dynamics of photo‐burst movement (induced by [2+2] photocycloaddition) and photochromism (induced by photogenerated radicals) in a bismuth (Bi)‐based metal‐organic halide (MOH), a continuous and photo‐responsive ultralong RTP can be achieved. Furthermore, utilizing the same Bi‐based MOH, diverse application demonstrations, such as multi‐mode anti‐counterfeiting and information encryption, can be easily implemented. This work thus not only serves as a proof‐of‐concept for the development of solid‐state PCCPs that integrate photosalient effect and photochromism with light‐chemical‐mechanical energy conversion, but also lays the groundwork for designing new Bi‐based MOHs with dynamically responsive ultralong RTP. [ABSTRACT FROM AUTHOR]

We present an efficient method based on an extension of metadynamics for exploring complex free energy landscapes (FELs). The method employs two-step metadynamics simulations. In the first step, rapid metadynamics simulations using broad and tall Gaussians are performed to identify a free energy pathway (FEP) connecting the two states of interest. The FEP is then divided into a series of independent subphase spaces that comprise selected discrete images of the system. Using appropriate collective variables (CVs) chosen according to the FEP, the accurate FEL of each subphase space is separately calculated in subsequent divide-and-conquer metadynamics simulations with narrow and low Gaussians. Finally, all FELs calculated in each subphase space are merged to obtain the full FEL. We show that the method greatly improves the performance of the metadynamics approach. In particular, we are able to efficiently model chemical systems with complex FELs, such as chemical reactions at the air/water interface. We demonstrate the performance of this method on two model reactions: the hydrolysis of formaldehyde in the gas phase and at the air/water interface. [ABSTRACT FROM AUTHOR]

Reactive uptake of dinitrogen pentaoxide (N2O5) into aqueous aerosols is a major loss channel for NOx in the troposphere; however, a quantitative understanding of the uptake mechanism is lacking. Herein, a computational chemistry strategy is developed employing high-level quantum chemical methods; the method offers detailed molecular insight into the hydrolysis and ammonolysis mechanisms of N2O5 in microdroplets. Specifically, our calculations estimate the bulk and interfacial hydrolysis rates to be (2.3 ± 1.6) × 10−3 and (6.3 ± 4.2) × 10−7 ns−1, respectively, and ammonolysis competes with hydrolysis at NH3 concentrations above 1.9 × 10−4 mol L−1. The slow interfacial hydrolysis rate suggests that interfacial processes have negligible effect on the hydrolysis of N2O5 in liquid water. In contrast, N2O5 ammonolysis in liquid water is dominated by interfacial processes due to the high interfacial ammonolysis rate. Our findings and strategy are applicable to high-chemical complexity microdroplets.The authors report a computational strategy to simulate the hydrolysis and ammonolysis of N2O5 in aerosols using high-level quantum chemical methods. The computational results reveal a complete picture of the reactive uptake of N2O5 by atmospheric aerosols with or without NH3. [ABSTRACT FROM AUTHOR]

It was experimentally found that the gold-catalyzed reaction between o-alkynylphenols and aryldiazonium salts can lead to different products under thermo- and photocatalytic conditions; however, the mechanism is elusive. Herein we have employed both MS-CASPT2 and DFT approaches to study the catalytic mechanisms of the corresponding light- and thermal-driven reactions. The results show that both the thermo- and photo-catalytic reactions share some same elementary steps from the Au(I) catalyst and o-alkynylphenol, both of which generate a vinyl Au(I) intermediate with the aid of HCO3−. In these steps, the formation of a structurally distorted complex of the Au(I) catalyst and o-alkynylphenol has a free energy barrier of 14.8 kcal/mol in that the C≡C triple bond of o-alkynylphenol is seriously activated. Importantly, the thermo- and photo- catalytic reactions start to diverge from the complex formed between the generated vinyl Au(I) intermediate and the aryldiazonium salt. Under the dark condition, the reaction proceeds to generate the final thermal product after overcoming a free energy barrier of 15.7 kcal/mol, in which the terminal N atom of the aryldiazonium salt is bonded directly to the C atom of the Au(I) species. In the photoirradiation condition, the complex is first excited to its electronically excited singlet state, which then decays to the T1 state with an efficient intersystem crossing process of 9.8x109 s−1. In the T1 state, the denitrogen process completes easily after overcoming a free energy barrier of 7.8 kcal/mol resulting into an aryl radical interacting with the Au atom of the vinyl Au(I) species, which is followed by another intersystem crossing process from T1 to S0. In the S0 state, the final photocatalytic product is formed. The present work provides important mechanistic details on understanding both thermo- and photo-catalytic reactions of Au(I) catalysts and aryldiazonium salts, and most importantly, it is found that nonradiative transitions play an essential role in regulating photocatalytic reactions. [ABSTRACT FROM AUTHOR]

Photocatalytic CO2 reduction is one of the best solutions to solve the global energy crisis and to realize carbon neutralization. The tetradentate phosphine‐bipyridine (bpy)‐phosphine (PNNP)‐type Ir(III) photocatalyst, Mes‐IrPCY2, was reported with a high HCOOH selectivity but the photocatalytic mechanism remains elusive. Herein, we employ electronic structure methods in combination with radiative, nonradiative, and electron transfer rate calculations, to explore the entire photocatalytic cycle to either HCOOH or CO, based on which a new mechanistic scenario is proposed. The catalytic reduction reaction starts from the generation of the precursor metal‐to‐ligand charge transfer (3MLCT) state. Subsequently, the divergence happens from the 3MLCT state, the single electron transfer (SET) and deprotonation process lead to the formation of one‐electron‐reduced species and Ir(I) species, which initiate the reduction reaction to HCOOH and CO, respectively. Interestingly, the efficient occurrence of proton or electron transfer reduces barriers of critical steps. In addition, nonadiabatic transitions play a nonnegligible role in the cycle. We suggest a lower free‐energy barrier in the reaction‐limiting step and the very efficient SET in 3MLCT are cooperatively responsible for a high HCOOH selectivity. The gained mechanistic insights could help chemists to understand, regulate, and design photocatalytic CO2 reduction reaction of similar function‐integrated molecular photocatalyst. [ABSTRACT FROM AUTHOR]