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It is well-known experimentally that the positively charged muon and the muonium atom may bind to molecules and solids, and through muon's magnetic interaction with unpaired electrons, valuable information on the local environment surrounding the muon is deduced. Theoretical understanding of the structure and properties of resulting muonic species requires accurate and efficient quantum mechanical computational methodologies. In this paper, the two-component density functional theory (TC-DFT), as a first principles method, which treats electrons and the positive muon on an equal footing as quantum particles, is introduced and implemented computationally. The main ingredient of this theory, apart from the electronic exchange–correlation functional, is the electron–positive muon correlation functional that is foreign to the purely electronic DFT. A Wigner-type local electron–positive muon correlation functional, termed eμc-1, is proposed in this paper and its capability is demonstrated through its computational application to a benchmark set of muonic organic molecules. The TC-DFT equations containing eμc-1 are not only capable of predicting the muon's binding site correctly, but they also reproduce muon's zero-point vibrational energies and the muonic densities much more accurately than the TC-DFT equations lacking eμc-1. Thus, this study sets the stage for developing accurate electron–positive muon functionals, which can be used within the context of the TC-DFT to elucidate the intricate interaction of the positive muon with complex molecular systems. [ABSTRACT FROM AUTHOR]

We obtain the phase diagram of the hard core lattice gas with third nearest neighbor exclusion on the triangular lattice using Monte Carlo simulations that are based on a rejection-free flat histogram algorithm. In a recent paper [Darjani et al., J. Chem. Phys. 151, 104702 (2019)], it was claimed that the lattice gas with third nearest neighbor exclusion undergoes two phase transitions with increasing density with the phase at intermediate densities exhibiting hexatic order with continuously varying exponents. Although a hexatic phase is expected when the exclusion range is large, it has not been seen earlier in hard core lattice gases with short range exclusion. In this paper, by numerically determining the entropies for all densities, we show that there is only a single phase transition in the system between a low-density fluid phase and a high density ordered sublattice phase and that a hexatic phase is absent. The transition is shown to be first order in nature, and the critical parameters are determined accurately. [ABSTRACT FROM AUTHOR]

In recent papers, Becke et al. [J. Chem. Phys. 158, 151103 (2023)] and then Becke [J. Chem. Phys. 159, 241101 (2023)] have developed a novel double hybrid density functional, "DH23," whose terms are based on good local physics. Its 12 coefficients are trained on the GMTKN55 (general main-group thermochemistry, kinetics, and noncovalent interactions) chemical database of Goerigk et al. [Phys. Chem. Chem. Phys. 19, 32184 (2017)]. The lowest GMTKN55 "WTMAD2" error to date for any hybrid or double hybrid density functional was obtained (1.73 kcal/mol for the revDH23 variant). Here, we simplify DH23 by introducing a dispersion damping scheme involving atomic numbers only and one global parameter. The resulting new functional, "DH24," performs as well as its predecessors. [ABSTRACT FROM AUTHOR]

In this paper, benchmark results are presented on the calculation of vertical electronic excitation energies using a long-range second-order polarization propagator approximation (SOPPA) description with a short-range density functional theory description based on the Perdew–Burke–Ernzerhof (PBE) functional. The excitation energies are investigated for 132 singlet states and 71 triplet states across 28 medium-sized organic molecules. The results show that overall SOPPA-srPBE always performs better than PBE and that SOPPA-srPBE performs better than SOPPA for singlet states, but slightly worse than SOPPA for triplet states when CC3 results are the reference values. [ABSTRACT FROM AUTHOR]

In this paper, we present a combined experimental and theoretical study that explored the initial sticking of water on cooled surfaces. Specifically, these ultra-high vacuum gas–surface scattering experiments utilized supersonic molecular beam techniques in conjunction with a cryogenically cooled highly oriented pyrolytic graphite crystal, giving control over incident kinematic conditions. The D2O translational energy spanning 300–750 meV, the relative D2O flux, and the incident angle could all be varied independently. Three different experimental measurements were made. One involved measuring the total amount of D2O scattering as a function of surface temperature to determine the onset of sticking under non-equilibrium gas–surface collision conditions. Another measurement used He specular scattering to assess structural and coverage information for the interface during D2O adsorption. Finally, we used time-of-flight (TOF) measurements of the scattered D2O to determine how energy is exchanged with the graphite surface at surface temperatures above and near the conditions needed for gaseous condensation. For comparison and elaboration of the roles that internal degrees of freedom play in this process, we also did similar TOF measurements using another mass 20 incident particle, atomic neon. Enriching this study are precise molecular dynamics simulations that elaborate on gas–surface energy transfer and the roles of molecular degrees of freedom in gas–surface collisional energy exchange processes. This study furthers our fundamental understanding of energy exchange and the onset of sticking and ultimately gaseous condensation for gas–surface encounters occurring under high-velocity flows. [ABSTRACT FROM AUTHOR]

This paper reports on the effects of shear rate and interface modeling parameters on the hydrodynamic slip length (LS) for water–graphite interfaces calculated using non-equilibrium molecular dynamics. Five distinct non-bonded solid–liquid interaction parameters were considered to assess their impact on LS. The interfacial force field derivations included sophisticated electronic structure calculation-informed and empirically determined parameters. All interface models exhibited a similar and bimodal LS response when varying the applied shear rate. LS in the low shear rate regime (LSR) is in good agreement with previous calculations obtained through equilibrium molecular dynamics. As the shear rate increases, LS sharply increases and asymptotes to a constant value in the high shear regime (HSR). It is noteworthy that LS in both the LSR and HSR can be characterized by the density depletion length, whereas solid–liquid adhesion metrics failed to do so. For all interface models, LHSR calculations were, on average, ∼28% greater than LLSR, and this slip jump was confirmed using the SPC/E and TIP4P/2005 water models. To address the LS transition from the LSR to the HSR, the viscosity of water and the interfacial friction coefficient were investigated. It was observed that in the LSR, the viscosity and friction coefficient decreased at a similar rate, while in the LSR-to-HSR transition, the friction coefficient decreased at a faster rate than the shear viscosity until they reached a new equilibrium, hence explaining the LS-bimodal behavior. This study provides valuable insights into the interplay between interface modeling parameters, shear rate, and rheological properties in understanding hydrodynamic slip behavior. [ABSTRACT FROM AUTHOR]

The combination of vibrational perturbation theory with the replacement of the harmonic oscillator quantization condition along the reaction coordinate with an imaginary action to be used in the uniform semiclassical approximation for the transmission probability has been shown in recent years to be a practical method for obtaining thermal reaction rates. To date, this theory has been developed systematically only up to second order in perturbation theory. Although it gives the correct leading order term in an ℏ2 expansion, its accuracy at lower temperatures, where tunneling becomes important, is not clear. In this paper, we develop the theory to fourth order in the action. This demands developing the quantum perturbation theory up to sixth order. Remarkably, we find that the fourth order theory gives the correct ℏ4 term in the expansion of the exact thermal rate. The relative magnitude of the fourth order correction as compared to the second order term objectively indicates the accuracy of the second order theory. We also extend the previous modified second order theory to the fourth order case, creating an ℏ2 modified potential for this purpose. The resulting theory is tested on the standard examples—symmetric and asymmetric Eckart potentials and a Gaussian potential. The modified fourth order theory is remarkably accurate for the asymmetric Eckart potential. [ABSTRACT FROM AUTHOR]

Several enhanced sampling techniques rely on the definition of collective variables to effectively explore free energy landscapes. The existing variables that describe the progression along a reactive pathway offer an elegant solution but face a number of limitations. In this paper, we address these challenges by introducing a new path-like collective variable called the "deep-locally non-linear-embedding," which is inspired by principles of the locally linear embedding technique and is trained on a reactive trajectory. The variable mimics the ideal reaction coordinate by automatically generating a non-linear combination of features through a differentiable generalized autoencoder that combines a neural network with a continuous k-nearest neighbor selection. Among the key advantages of this method is its capability to automatically choose the metric for searching neighbors and to learn the path from state A to state B without the need to handpick landmarks a priori. We demonstrate the effectiveness of DeepLNE by showing that the progression along the path variable closely approximates the ideal reaction coordinate in toy models, such as the Müller-Brown potential and alanine dipeptide. Then, we use it in the molecular dynamics simulations of an RNA tetraloop, where we highlight its capability to accelerate transitions and estimate the free energy of folding. [ABSTRACT FROM AUTHOR]

Coarse-grained (CG) molecular models greatly reduce the computational cost of simulations allowing for longer and larger simulations, but come with an artificially increased acceleration of the dynamics when compared to the parent atomistic (AA) simulation. This impedes their use for the quantitative study of dynamical properties. During coarse-graining, grouping several atoms into one CG bead not only reduces the number of degrees of freedom but also reduces the roughness on the molecular surfaces, leading to the acceleration of dynamics. The RoughMob approach [M. K. Meinel and F. Müller-Plathe, J. Phys. Chem. B 126(20), 3737–3747 (2022)] quantifies this change in geometry and correlates it to the acceleration by making use of four so-called roughness volumes. This method was developed using simple one-bead CG models of a set of hydrocarbon liquids. Potentials for pure components are derived by the structure-based iterative Boltzmann inversion. In this paper, we find that, for binary mixtures of simple hydrocarbons, it is sufficient to use simple averaging rules to calculate the roughness volumes in mixtures from the roughness volumes of pure components and add a correction term quadratic in the concentration without the need to perform any calculation on AA or CG trajectories of the mixtures themselves. The acceleration factors of binary diffusion coefficients and both self-diffusion coefficients show a large dependence on the overall acceleration of the system and can be predicted a priori without the need for any AA simulations within a percentage error margin, which is comparable to routine measurement accuracies. Only if a qualitatively accurate description of the concentration dependence of the binary diffusion coefficient is desired, very few additional simulations of the pure components and the equimolar mixture are required. [ABSTRACT FROM AUTHOR]

In nonequilibrium statistical physics, quantifying the nearest (and higher-order) neighbors and free volumes of particles in many-body systems is crucial to elucidating the origin of macroscopic collective phenomena, such as glass/granular jamming transitions and various aspects of the behavior of active matter. However, conventional techniques (based on a fixed-distance cutoff or the Voronoi construction) have mainly been applied to equilibrated, homogeneous, and monodisperse particle systems. In this paper, we implement simple and efficient methods for local structure analysis in nonequilibrium, inhomogeneous, and polydisperse hard disk systems. We show how these novel methods can overcome the difficulties encountered by conventional techniques as well as demonstrate some applications. [ABSTRACT FROM AUTHOR]

Produced by both nature and human activities, sulfur dioxide (SO2) is an important species in the earth's atmosphere. SO2 has also been found in the atmospheres of other planets and satellites in the solar system. The photoabsorption cross sections and photodissociation of SO2 have been studied for several decades. In this paper, we reported the experimental results for photodissociation dynamics of SO2 via the G ̃ 1B1 state. By analyzing the images from the time-sliced velocity map ion imaging method, the vibrational state population distributions and anisotropy parameters were obtained for the O(1D2) + SO(X3Σ−, a1Δ, b1Σ+) and O(1S0) + SO(X3Σ−) channels, and the branching ratios for the channels O(1D2) + SO(X3Σ−), O(1D2) + SO(a1Δ), and O(1D2) + SO(b1Σ+) were determined to be ∼0.3, ∼0.6, and ∼0.1, respectively. The SO products were dominant in electronically and rovibrationally excited states, which may have yet unrecognized roles in the upper planetary atmosphere. [ABSTRACT FROM AUTHOR]

Molecular chirality has traditionally been viewed as a binary property where a molecule is classified as either chiral or achiral, yet in recent decades, mathematical methods for quantifying chirality have been explored. Here, we use toy molecular systems to systematically compare the performance of two state-of-the-art chirality measures: (1) the Continuous Chirality Measure (CCM) and (2) the Chirality Characteristic (χ). We find that both methods exhibit qualitatively similar behavior when applied to simple molecular systems such as a four-site molecule or the polymer double-helix, but we show that the CCM may be more suitable for evaluating the chirality of arbitrary molecules or abstract structures such as normal vibrational modes. We discuss a range of considerations for applying these methods to molecular systems in general, and we provide links to user-friendly codes for both methods. We aim for this paper to serve as a concise resource for scientists attempting to familiarize themselves with these chirality measures or attempting to implement chirality measures in their own work. [ABSTRACT FROM AUTHOR]

Semiconductor nanocrystals (NCs) can function as efficient gain materials with chemical versatility because of their surface ligands. Because the properties of NCs in solution are sensitive to ligand–environment interactions, local chemical changes can result in changes in the optical response. However, amplification of the optical response is technically challenging because of colloidal instability at NC concentrations needed for sufficient gain to overcome losses. This paper demonstrates liquid lasing from plasmonic lattice cavities integrated with ligand-engineered CdZnS/ZnS NCs dispersed in toluene and water. By taking advantage of calcium ion-induced aggregation of NCs in aqueous solutions, we show how lasing threshold can be used as a transduction signal for ion detection. Our work highlights how NC solutions and plasmonic lattices with open cavity architectures can serve as a biosensing platform for lab-on-chip devices. [ABSTRACT FROM AUTHOR]

Chemical shakers are active particles with zero propulsion velocity whose activity derives from chemical reactions on portions of their surfaces. Although they do not move, except through Brownian motion, the nonequilibrium concentration and velocity fields that they generate endow them with properties that differ from their equilibrium counterparts. In particular, collections of such shakers can actively move, reorient, and self-assemble into various cluster states, which are the subject of this paper. Elongated chemical shakers constructed from linked catalytic and noncatalytic spheres are considered, and it is shown how hydrodynamic, chemotactic, and shape-dependent interactions give rise to various self-assembled shaker structures. The chemical forces responsible for cluster formation are described in terms of a model based on pair-wise additive contributions. The forms of the self-assembled structures can be varied by changing the chemostat concentrations that control the nonequilibrium state. The resulting structures and their manipulation through chemical means suggest ways to construct a class of active materials for applications. [ABSTRACT FROM AUTHOR]

Packaging insulation materials with high thermal conductivity and excellent dielectric properties are favorable to meet the high demand and rapid development of third generation power semiconductors. In this study, we propose to improve the thermal conductivity of epoxy resin (EP) by incorporating a three-dimensional boron nitride thermally conductive network. Detailedly, polyurethane foam (PU) was used as a supporter, and boron nitride nanosheets (BNNSs) were loaded onto the PU supporter through chemical bonding (BNNS@PU). After immersing BNNS@PU into the EP resin, EP-based thermally conductive composites were prepared by vacuum-assisted impregnation. Fourier transform infrared spectrometer and scanning electron microscope were used to characterize the chemical bonding and morphological structure of BNNS@PU, respectively. The content of BNNS in BNNS@PU/EP composites was quantitatively analyzed by TGA. The results show that the thermal conductivity of the BNNS@PU/EP composites reaches 0.521 W/m K with an enhancement rate η of 30.89 at an ultra-low BNNS filler content (5.93 wt. %). Additionally, the BNNS@PU/EP composites have excellent dielectric properties with the frequency range from 101 to 106 Hz. This paper provides an interesting idea for developing high thermal conductivity insulating materials used for power semiconductor packaging. [ABSTRACT FROM AUTHOR]

This paper explores the unintentional contamination of Surface-Enhanced Raman Scattering (SERS) substrates by ambient hydrocarbon contaminants and their contribution to SERS spectra. Previous studies have identified amorphous carbon as a potential complicating factor in data analysis in SERS experiments, although its origin has been elusive. Our work showed that ambient hydrocarbon contamination and its decomposition products can be detected by SERS on a gold substrate. We propose that ambient air itself is a source of amorphous carbon contamination on SERS substrates. This understanding is crucial for the correct interpretation of SERS data and highlights the need for careful consideration of potential environmental contaminants in SERS analysis. [ABSTRACT FROM AUTHOR]

In this paper, the responses of assembled behaviors of block polyelectrolytes (PEs) to the strength of electrostatic interactions are studied through molecular dynamic simulations. The results show that the assembled structures closely depend on the electrostatic strength. It should be noted that PE coacervation can outweigh the nucleation of hydrophobic blocks and invert the micelle structures at strong electrostatic strengths, leading to the formation of inverted micelles of PE cores and hydrophobic coronas. In the poor solvent condition for neutral block, diverse anisotropic micelles are presented; candy-like conventional micelles of hydrophobic cores and PE patches coexist with inverted candy-like micelles of PE cores and hydrophobic patches and with Janus micelles of semi-neutral aggregate and semi-PE cluster in the presence of divalent and trivalent counterions. The formation of conventional or inverted micelle is largely determined by the type of micellar fusion, which results from the nucleation competition between electrostatic correlation and hydrophobic interaction. The merge of micelles mediated by hydrophobic attraction leads to conventional hydrophobic cores, and the fusion induced by electrostatic correlations results in PE cores micelles. At strong electrostatic strengths, the PE chains exhibit rich conformations at trivalent counterions, ranging from a fully collapsed state to a rod-like state, and parallel alignment of PE chains is found. [ABSTRACT FROM AUTHOR]

Ion channels are proteins that play a significant role in physiological processes, including neuronal excitability and signal transduction. However, the precise mechanisms by which these proteins facilitate ion diffusion through cell membranes are not well understood. This is because experimental techniques to characterize ion channel activity operate on a time scale too large to understand the role of the various protein conformations on diffusion. Meanwhile, computational approaches operate on a time scale too short to rationalize the observed behavior at the microscopic scale. In this paper, we present a continuous-time random walk model that aims to bridge the scales between the atomistic models of ion channels and the experimental measurement of their conductance. We show how diffusion slows down in complex systems by using 3D lattices that map out the pore geometry of two channels: Nav1.7 and gramicidin. We also introduce spatial and dynamic site disorder to account for system heterogeneity beyond the mean field approximation. Computed diffusion coefficients show that an increase in spatial disorder slows down diffusion kinetics, while dynamic disorder has the opposite effect. Our results imply that microscopic or phenomenological models based on the potential of mean force data overlook the functional importance of protein dynamics on ion diffusion through channels. [ABSTRACT FROM AUTHOR]

Conical intersection (CI) leads to fast electronic energy transfer. However, Hamm and Stock [Phys. Rev. Lett. 109, 173201 (2012)] showed the existence of a vibrational CI and its role in vibrational energy relaxation. In this paper, we further investigate the vibrational energy relaxation using an isolated model Hamiltonian system of four vibrational modes with two distinctively different timescales (two fast modes and two slow modes). We show that the excitation of the slow modes plays a crucial role in the energy relaxation mechanism. We also analyze the system from a mixed quantum-classical (surface hopping method) and a completely classical point of view. Notably, surface hopping and even classical simulations also capture fast energy relaxation, which is a signature of CI's existence. [ABSTRACT FROM AUTHOR]

This paper introduces a spin-free formulation of the supporting subspace factorization [C. Song and T. J. Martínez, J. Chem. Phys. 149, 044108 (2018)], enabling a reduction in the computational scaling of the extended multi-state complete active space second-order perturbation (XMS-CASPT2) method for arbitrary spins. Compared to the original formulation that is defined in the spin orbitals and is limited to singlet states, the spin-free formulation in this work treats different spin states equivalently, thus naturally generalizing the idea beyond singlet states. In addition, we will present a new way of deriving the supporting subspace factorization with the purpose of understanding its physical interpretation. In this new derivation, we separate the sources that make CASPT2 difficult into the "same-site interactions" and "inter-site interactions." We will first show how the Kronecker sum can be used to remove the same-site interactions in the absence of inter-site interactions, leading to MP2 energy in dressed orbitals. We will then show how the inter-site interactions can be exactly recovered using Löwdin partition, where the supporting subspace concept will naturally arise. The new spin-free formulation maintains the main advantage of the supporting subspace factorization, i.e., allowing XMS-CASPT2 energies to be computed using highly optimized MP2 energy codes and Fock build codes, thus reducing the scaling of XMS-CASPT2 to the same scaling as MP2. We will present and discuss results that benchmark the accuracy and performance of the new method. To demonstrate how the new method can be useful in studying real photochemical systems, the supporting subspace XMS-CASPT2 is applied to a photoreaction sensitive to magnetic field effects. The new spin-free formulation makes it possible to calculate the doublet and quartet states required in this particular photoreaction mechanism. [ABSTRACT FROM AUTHOR]

Alchemical transformations showed that perturbation theory can be applied also to changes in the atomic nuclear charges of a molecule. The alchemical path that connects two different chemical species involves the conceptualization of a non-physical system in which an atom possess a non-integer nuclear charge. A correct quantum mechanical treatment of these systems is limited by the fact that finite size atomic basis sets do not define exponents and contraction coefficients for fractional charge atoms. This paper proposes a solution to this problem and shows that a smooth interpolation of the atomic orbital coefficients and exponents across the periodic table is a convenient way to produce accurate alchemical predictions, even using small size basis sets. [ABSTRACT FROM AUTHOR]

Within the context of fewest-switch surface hopping (FSSH) dynamics, one often wishes to remove the angular component of the derivative coupling between states J and K . In a previous set of papers, Shu et al. [J. Phys. Chem. Lett. 11, 1135–1140 (2020)] posited one approach for such a removal based on direct projection, while we isolated a second approach by constructing and differentiating a rotationally invariant basis. Unfortunately, neither approach was able to demonstrate a one-electron operator O ̂ whose matrix element J O ̂ K was the angular component of the derivative coupling. Here, we show that a one-electron operator can, in fact, be constructed efficiently in a semi-local fashion. The present results yield physical insight into designing new surface hopping algorithms and are of immediate use for FSSH calculations. [ABSTRACT FROM AUTHOR]

To address the challenge of performance portability and facilitate the implementation of electronic structure solvers, we developed the basic matrix library (BML) and Parallel, Rapid O(N), and Graph-based Recursive Electronic Structure Solver (PROGRESS) library. The BML implements linear algebra operations necessary for electronic structure kernels using a unified user interface for various matrix formats (dense and sparse) and architectures (CPUs and GPUs). Focusing on density functional theory and tight-binding models, PROGRESS implements several solvers for computing the single-particle density matrix and relies on BML. In this paper, we describe the general strategies used for these implementations on various computer architectures, using OpenMP target functionalities on GPUs, in conjunction with third-party libraries to handle performance critical numerical kernels. We demonstrate the portability of this approach and its performance in benchmark problems. [ABSTRACT FROM AUTHOR]

The diffusion of dilute molecular penetrants within polymers plays a crucial role in the advancement of material engineering for applications such as coatings and membrane separations. The potential of highly cross-linked polymer networks in these applications stems from their capacity to adjust the size and shape selectivity through subtle changes in network structures. In this paper, we use molecular dynamics simulation to understand the role of penetrant shape (aspect ratios) and its interaction with polymer networks on its diffusivity. We characterize both local penetrant hopping and the long-time diffusive motion for penetrants and consider different aspect ratios and penetrant–network interaction strengths at a variety of cross-link densities and temperatures. The shape affects the coupling of penetrant motion to the cross-link density- and temperature-dependent structural relaxation of networks and also affects the way a penetrant experiences the confinement from the network meshes. The attractive interaction between the penetrant and network primarily affects the former since only the system of dilute limit is of present interest. These results offer fundamental insights into the intricate interplay between penetrant characteristics and polymer network properties and also suggest future directions for manipulating polymer design to enhance the separation efficiency. [ABSTRACT FROM AUTHOR]

In this paper, we investigate the performance of different machine learning potentials (MLPs) in predicting key thermodynamic properties of water using RPBE + D3. Specifically, we scrutinize kernel-based regression and high-dimensional neural networks trained on a highly accurate dataset consisting of about 1500 structures, as well as a smaller dataset, about half the size, obtained using only on-the-fly learning. This study reveals that despite minor differences between the MLPs, their agreement on observables such as the diffusion constant and pair-correlation functions is excellent, especially for the large training dataset. Variations in the predicted density isobars, albeit somewhat larger, are also acceptable, particularly given the errors inherent to approximate density functional theory. Overall, this study emphasizes the relevance of the database over the fitting method. Finally, this study underscores the limitations of root mean square errors and the need for comprehensive testing, advocating the use of multiple MLPs for enhanced certainty, particularly when simulating complex thermodynamic properties that may not be fully captured by simpler tests. [ABSTRACT FROM AUTHOR]

This article describes a method for calculating higher order or nonadiabatic corrections in Born–Oppenheimer theory and its interaction with the translational degrees of freedom. The method uses the Wigner–Weyl correspondence to map nuclear operators into functions on the classical phase space and the Moyal star product to represent operator multiplication on those functions. These are explained in the body of the paper. The result is a power series in κ2, where κ = (m/M)1/4 is the usual Born–Oppenheimer parameter. The lowest order term is the usual Born–Oppenheimer approximation, while higher order terms are nonadiabatic corrections. These are needed in calculations of electronic currents, momenta, and densities. The separation of nuclear and electronic degrees of freedom takes place in the context of the exact symmetries (for an isolated molecule) of translations and rotations, and these, especially translations, are explicitly incorporated into our discussion. This article presents an independent derivation of the Moyal expansion in molecular Born–Oppenheimer theory. We show how electronic currents and momenta can be calculated within the framework of Moyal perturbation theory; we derive the transformation laws of the electronic Hamiltonian, the electronic eigenstates, and the derivative couplings under translations; we discuss in detail the rectilinear motion of the molecular center of mass in the Born–Oppenheimer representation; and we show how the elimination of the translational components of the derivative couplings leads to a unitary transformation that has the effect of exactly separating the translational degrees of freedom. [ABSTRACT FROM AUTHOR]

Time-Resolved Serial Femtosecond Crystallography (TR-SFX) conducted at X-ray Free Electron Lasers (XFELs) has become a powerful tool for capturing macromolecular structural movies of light-initiated processes. As the capabilities of XFELs advance, we anticipate that a new range of coherent control and structural Raman measurements will become achievable. Shorter optical and x-ray pulse durations and increasingly more exotic pulse regimes are becoming available at free electron lasers. Moreover, with high repetition enabled by the superconducting technology of European XFEL (EuXFEL) and Linac Coherent Light Source (LCLS-II) , it will be possible to improve the signal-to-noise ratio of the light-induced differences, allowing for the observation of vibronic motion on the sub-Angstrom level. To predict and assign this coherent motion, which is measurable with a structural technique, new theoretical approaches must be developed. In this paper, we present a theoretical density matrix approach to model the various population and coherent dynamics of a system, which considers molecular system parameters and excitation conditions. We emphasize the use of the Wigner transform of the time-dependent density matrix, which provides a phase space representation that can be directly compared to the experimental positional displacements measured in a TR-SFX experiment. Here, we extend the results from simple models to include more realistic schemes that include large relaxation terms. We explore a variety of pulse schemes using multiple model systems using realistic parameters. An open-source software package is provided to perform the density matrix simulation and Wigner transformations. The open-source software allows us to define any arbitrary level schemes as well as any arbitrary electric field in the interaction Hamiltonian. [ABSTRACT FROM AUTHOR]

Protein–calixarenes binding plays an increasingly central role in many applications, spanning from molecular recognition to drug delivery strategies and protein inhibition. These ligands obey a specific bio-supramolecular chemistry, which can be revealed by computational approaches, such as molecular dynamics simulations. In this paper, we rely on all-atom, explicit-solvent molecular dynamics simulations to capture the electrostatically driven association of a phosphonated calix-[4]-arene with cytochome-C, which critically relies on surface-exposed paired lysines. Beyond two binding sites identified in direct agreement with the x-ray structure, the association has a larger structural impact on the protein dynamics. Then, our simulations allow a direct comparison to analogous calixarenes, namely, sulfonato, similarly reported as "molecular glue." Our work can contribute to a robust in silico predictive tool to assess binding sites for any given protein of interest for crystallization, with the specificity of a macromolecular cage whose endo/exo orientation plays a role in the binding. [ABSTRACT FROM AUTHOR]

We introduce a generalized micro–macro Markov chain Monte Carlo (mM-MCMC) method with pseudo-marginal approximation to the free energy that is able to accelerate sampling of the microscopic Gibbs distributions when there is a time-scale separation between the macroscopic dynamics of a reaction coordinate and the remaining microscopic degrees of freedom. The mM-MCMC method attains this efficiency by iterating four steps: (i) propose a new value of the reaction coordinate, (ii) accept or reject the macroscopic sample, (iii) run a biased simulation that creates a microscopic molecular instance that lies close to the newly sampled macroscopic reaction coordinate value, and (iv) microscopic accept/reject step for the new microscopic sample. In the present paper, we eliminate the main computational bottleneck of earlier versions of this method: the necessity to have an accurate approximation of free energy. We show that the introduction of a pseudo-marginal approximation significantly reduces the computational cost of the microscopic accept/reject step while still providing unbiased samples. We illustrate the method's behavior on several molecular systems with low-dimensional reaction coordinates. [ABSTRACT FROM AUTHOR]

In this paper, we develop and analyze a number of perturbation series that target the coupled cluster singles and doubles (CCSD) ground state energy. We show how classical Møller–Plesset perturbation theory series can be restructured to target the CCSD energy based on a reference CCS calculation and how the corresponding cluster perturbation series differs from the classical Møller–Plesset perturbation series. Subsequently, we reformulate these series using the coupled cluster Lagrangian framework to obtain series, where fourth and fifth order energies are determined only using parameters through second order. To test the methods, we perform a series of test calculations on molecular photoswitches of both total energies and reaction energies. We find that the fifth order reaction energies are of CCSD quality and that they are of comparable accuracy to state-of-the-art approximations to the CCSD energy based on local pair natural orbitals. The advantage of the present approach over local correlation methods is the absence of user defined threshold parameters for neglecting or approximating contributions to the correlation energy. Fixed threshold parameters lead to discontinuous energy surfaces, although this effect is often small enough to be ignored, but the present approach has a differentiable energy that will facilitate derivation and implementation of gradients and higher derivatives. A further advantage is that the calculation of the perturbation correction is non-iterative and can, therefore, be calculated in parallel, leading to a short time-to-solution. [ABSTRACT FROM AUTHOR]

The large discrepancy among the nucleation kinetics extracted from experimental measurements and computer simulations and the prediction of the classical nucleation theory (CNT) has stimulated intense arguments about its origin in the past decades, which is crucially relevant to the validity of the CNT. In this paper, we investigate the atomistic mechanism of the nucleation in liquid Al in contact with amorphous substrates with atomic-level smooth/rough surfaces, using molecular dynamics (MD) simulations. This study reveals that the slightly distorted local fcc/hcp structures in amorphous substrates with smooth surfaces can promote heterogeneous nucleation through a structural templating mechanism, and on the other hand, homogeneous nucleation will occur at a larger undercooling through a fluctuation mechanism if the surface is rough. Thus, some impurities, previously thought to be impotent, could be activated in the homogeneous nucleation experiments. We further find that the initial growth of the nucleus on smooth surfaces of amorphous substrates is one order of magnitude faster than that in homogeneous nucleation. Both these factors could significantly contribute to the discrepancy in the nucleation kinetics. This study is also supported by a recent study of the synthesis of high-entropy alloy nanoparticles assisted with the liquid metal Ga [Cao et al., Nature 619, 73 (2023)]. In this study, we established that the boundary existed between homogeneous and heterogeneous nucleation, i.e., the structural templating is a general mechanism for heterogeneous nucleation, and in its absence, homogeneous nucleation will occur through the fluctuation mechanism. This study provides an in-depth understanding of the nucleation theory and experiments. [ABSTRACT FROM AUTHOR]

In order to prepare highly heat-resistant packaging insulation materials, in this paper, bismaleimide/epoxy resin (BMI/EP55) composites with different contents of BMI were prepared by melt blending BMI into amino tetrafunctional and phenolic epoxy resin (at a ratio of 5:5). The microstructures and thermal and electrical properties of the composites were tested. The electrostatic potential distribution, energy level distribution, and molecular orbitals of BMI were calculated using Gaussian. The results showed that the carbonyl group in BMI is highly electronegative, implying that the carbonyl group has a strong electron trapping ability. The thermal decomposition temperature of the composites gradually increased with the increase of BMI content, and the 20% BMI/EP55 composites had the highest heat-resistance index, along with a glass transition temperature (Tg) of >250 °C. At different test temperatures, with increase in the BMI content, the conductivity of epoxy resin composites showed a tendency to first decrease and then increase, the breakdown field strength showed a tendency to first increase and then decrease, and the dielectric constant was gradually decreased. Two trap centers were present simultaneously in the composites, where the shallow trap energy level is the deepest in 20% BMI/EP composites and the deep trap energy level is the deepest in 10% BMI/EP55 composites. Correspondingly, the 10% BMI/EP55 composite had a slower charge decay rate, while the 20% BMI/EP55 had a faster charge decay rate. In summary, the BMI/EP55 composites with high heat resistance and insulating properties were prepared in this study, which provided ideas for preparing high-temperature packaging insulating materials. [ABSTRACT FROM AUTHOR]

Methyl nitrite has two stable conformational isomers resulting from rotation about the primary C–O–N–O dihedral angle: cis-CH3ONO and trans-CH3ONO, with cis being more stable by ∼5 kJ/mol. The barrier to rotational interconversion (∼45 kJ/mol) is too large for isomerization to occur under ambient conditions. This paper presents evidence of a change in conformer abundance when dilute CH3ONO is deposited onto a cold substrate; the relative population of the freshly deposited cis conformer is seen to increase compared to its gas-phase abundance, measured by in situ infrared spectroscopy. We observe abundance changes depending on the identity of the bath gas (N2, Ar, and Xe) and deposition angle. The observations indicate that the surface properties of the growing matrix influence conformer abundance—contrary to the widely held assumption that conformer abundance in matrices reflects gas-phase abundance. We posit that differences in the angle-dependent host-gas deposition dynamics affect the growing surfaces, causing changes in conformer abundances. Quantum chemistry calculations of the binding energies between CH3ONO and a single bath-gas component reveal that significant energetic stabilization is not observed in 1:1 complexes of N2:CH3ONO, Ar:CH3ONO, or Xe:CH3ONO. From our results, we conclude that the growing surface plays a significant role in trapping cis-CH3ONO more effectively than trans-CH3ONO, likely because cis-CH3ONO is more compact. Taken together, the observations highlight the necessity for careful characterization of conformers in matrix-isolated systems, emphasizing a need for further study into the deposition dynamics and surface structure of chemically inert matrices. [ABSTRACT FROM AUTHOR]

In this paper, we report on the implementation of CC2 and CC3 in the context of molecules in finite magnetic fields. The methods are applied to the investigation of atoms and molecules through spectroscopic predictions and geometry optimizations for the study of the atmosphere of highly magnetized White Dwarf stars. We show that ground-state finite-field (ff) CC2 is a reasonable alternative to CCSD for energies and, in particular, for geometrical properties. For excited states, ff-CC2 is shown to perform well for states with predominant single-excitation character. Yet, for cases in which the excited state wavefunction has double-excitation character with respect to the reference, ff-CC2 can easily lead to completely unphysical results. Ff-CC3, however, is shown to reproduce the CCSDT behavior very well and enables the treatment of larger systems at a high accuracy. [ABSTRACT FROM AUTHOR]

Conical intersections are known to play a vital role in many photochemical processes. The breakdown of the Born–Oppenheimer approximation in the vicinity of a conical intersection causes exciting phenomena, such as the ultrafast radiationless decay of excited states. The passage of a molecule through a conical intersection creates a coherent superposition of electronic states via nonadiabatic couplings. Detecting this coherent superposition may serve as a direct probe of the conical intersection. In this paper, we theoretically demonstrate the use of coherent spontaneous emission in samples with long-range order for probing the occurrence of a conical intersection in a molecule. Our simulations show that the spectrum contains clear signatures of the created coherent superposition of electronic states. We investigate the bandwidth requirements for the x-ray probes, which influence the observation of coherent superposition generated by the conical intersection. [ABSTRACT FROM AUTHOR]

A photovoltaic device fabricated with conventional zincblende materials can use the Type-II quantum well structure, which spatially separates electrons and holes, to reduce their recombination rate. In order to obtain higher power conversion efficiency, it is desirable to preserve more energetic carriers by engineering a phonon "bottleneck," a mismatch between the gaps in the well and barrier phonon structure. Such a mismatch leads to poor phonon transport and therefore prevents energy from leaving the system in the form of heat. In this paper, we perform a superlattice phonon calculation to verify the "bottleneck" effect and build on this a model to predict the steady state of the hot electrons under photoexcitation. We describe the electrons and phonons with a coupled Boltzmann equation system and numerically integrate it to get the steady state. We find that inhibited phonon relaxation does lead to a more out-of-equilibrium electron distribution and discuss how this might be enhanced. We examine the different behaviors obtained for various combinations of recombination and relaxation rates and their experimental signatures. [ABSTRACT FROM AUTHOR]

Simulations of exciton and charge hopping in amorphous organic materials involve numerous physical parameters. Each of these parameters must be computed from costly ab initio calculations before the simulation can commence, resulting in a significant computational overhead for studying exciton diffusion, especially in large and complex material datasets. While the idea of using machine learning to quickly predict these parameters has been explored previously, typical machine learning models require long training times, which ultimately contribute to simulation overheads. In this paper, we present a new machine learning architecture for building predictive models for intermolecular exciton coupling parameters. Our architecture is designed in such a way that the total training time is reduced compared to ordinary Gaussian process regression or kernel ridge regression models. Based on this architecture, we build a predictive model and use it to estimate the coupling parameters which enter into an exciton hopping simulation in amorphous pentacene. We show that this hopping simulation is able to achieve excellent predictions for exciton diffusion tensor elements and other properties as compared to a simulation using coupling parameters computed entirely from density functional theory. This result, along with the short training times afforded by our architecture, shows how machine learning can be used to reduce the high computational overheads associated with exciton and charge diffusion simulations in amorphous organic materials. [ABSTRACT FROM AUTHOR]

The self-consistent phonon (SCP) method allows one to include anharmonic effects when treating a many-body quantum system at thermal equilibrium. The system is then described by an effective temperature-dependent harmonic Hamiltonian, which can be used to estimate its various dynamic and static properties. In this paper, we combine SCP with ab initio (AI) potential energy evaluation in which case the numerical bottleneck of AI-SCP is the evaluation of Gaussian averages of the AI potential energy and its derivatives. These averages are computed efficiently by the quasi-Monte Carlo method utilizing low-discrepancy sequences leading to a fast convergence with respect to the number, S, of the AI energy evaluations. Moreover, a further substantial (an-order-of-magnitude) improvement in efficiency is achieved once a numerically cheap approximation of the AI potential is available. This is based on using a perturbation theory-like (the two-grid) approach in which it is the average of the difference between the AI and the approximate potential that is computed. The corresponding codes and scripts are provided. [ABSTRACT FROM AUTHOR]

A large number of force fields have been proposed for describing the behavior of liquid water within classical atomistic simulations, particularly molecular dynamics. In the past two decades, models that incorporate molecular polarizability and even charge transfer have become more prevalent, in attempts to develop more accurate descriptions. These are frequently parameterized to reproduce the measured thermodynamics, phase behavior, and structure of water. On the other hand, the dynamics of water is rarely considered in the construction of these models, despite its importance in their ultimate applications. In this paper, we explore the structure and dynamics of polarizable and charge-transfer water models, with a focus on timescales that directly or indirectly relate to hydrogen bond (H-bond) making and breaking. Moreover, we use the recently developed fluctuation theory for dynamics to determine the temperature dependence of these properties to shed light on the driving forces. This approach provides key insight into the timescale activation energies through a rigorous decomposition into contributions from the different interactions, including polarization and charge transfer. The results show that charge transfer effects have a negligible effect on the activation energies. Furthermore, the same tension between electrostatic and van der Waals interactions that is found in fixed-charge water models also governs the behavior of polarizable models. The models are found to involve significant energy–entropy compensation, pointing to the importance of developing water models that accurately describe the temperature dependence of water structure and dynamics. [ABSTRACT FROM AUTHOR]

Multiple ERI (Electron Repulsion Integral) tensor contractions (METC) with several matrices are ubiquitous in quantum chemistry. In response theories, the contraction operation, rather than ERI computations, can be the major bottleneck, as its computational demands are proportional to the multiplicatively combined contributions of the number of excited states and the kernel pre-factors. This paper presents several high-performance strategies for METC. Optimal approaches involve either the data layout reformations of interim density and Fock matrices, the introduction of intermediate ERI quartet buffer, and loop-reordering optimization for a higher cache hit rate. The combined strategies remarkably improve the performance of the MRSF (mixed reference spin flip)-TDDFT (time-dependent density functional theory) by nearly 300%. The results of this study are not limited to the MRSF-TDDFT method and can be applied to other METC scenarios. [ABSTRACT FROM AUTHOR]

In this paper, we outline a physically motivated framework for describing spin-selective recombination processes in chiral systems, from which we derive spin-selective reaction operators for recombination reactions of donor–bridge–acceptor molecules, where the electron transfer is mediated by chirality and spin–orbit coupling. In general, the recombination process is selective only for spin-coherence between singlet and triplet states, and it is not, in general, selective for spin polarization. We find that spin polarization selectivity only arises in hopping-mediated electron transfer. We describe how this effective spin-polarization selectivity is a consequence of spin-polarization generated transiently in the intermediate state. The recombination process also augments the coherent spin dynamics of the charge separated state, which is found to have a significant effect on the recombination dynamics and to destroy any long-lived spin polarization. Although we only consider a simple donor–bridge–acceptor system, the framework we present here can be straightforwardly extended to describe spin-selective recombination processes in more complex systems. [ABSTRACT FROM AUTHOR]

In this paper, the solubility of carbon dioxide (CO2) in water along the isobar of 400 bar is determined by computer simulations using the well-known TIP4P/Ice force field for water and the TraPPE model for CO2. In particular, the solubility of CO2 in water when in contact with the CO2 liquid phase and the solubility of CO2 in water when in contact with the hydrate have been determined. The solubility of CO2 in a liquid–liquid system decreases as the temperature increases. The solubility of CO2 in a hydrate–liquid system increases with temperature. The two curves intersect at a certain temperature that determines the dissociation temperature of the hydrate at 400 bar (T3). We compare the predictions with T3 obtained using the direct coexistence technique in a previous work. The results of both methods agree, and we suggest 290(2) K as the value of T3 for this system using the same cutoff distance for dispersive interactions. We also propose a novel and alternative route to evaluate the change in chemical potential for the formation of hydrates along the isobar. The new approach is based on the use of the solubility curve of CO2 when the aqueous solution is in contact with the hydrate phase. It considers rigorously the non-ideality of the aqueous solution of CO2, providing reliable values for the driving force for nucleation of hydrates in good agreement with other thermodynamic routes used. It is shown that the driving force for hydrate nucleation at 400 bar is larger for the methane hydrate than for the carbon dioxide hydrate when compared at the same supercooling. We have also analyzed and discussed the effect of the cutoff distance of dispersive interactions and the occupancy of CO2 on the driving force for nucleation of the hydrate. [ABSTRACT FROM AUTHOR]

The development of multireference coupled cluster (MRCC) techniques has remained an open area of study in electronic structure theory for decades due to the inherent complexity of expressing a multiconfigurational wavefunction in the fundamentally single-reference coupled cluster framework. The recently developed multireference-coupled cluster Monte Carlo (mrCCMC) technique uses the formal simplicity of the Monte Carlo approach to Hilbert space quantum chemistry to avoid some of the complexities of conventional MRCC, but there is room for improvement in terms of accuracy and, particularly, computational cost. In this paper, we explore the potential of incorporating ideas from conventional MRCC—namely, the treatment of the strongly correlated space in a configuration interaction formalism—to the mrCCMC framework, leading to a series of methods with increasing relaxation of the reference space in the presence of external amplitudes. These techniques offer new balances of stability and cost against accuracy, as well as a means to better explore and better understand the structure of solutions to the mrCCMC equations. [ABSTRACT FROM AUTHOR]

In this paper, we present a covariant approach that utilizes Noether's second theorem to derive a symmetric stress tensor from the grand thermodynamic potential functional. We focus on the practical case where the density of the grand thermodynamic potential is dependent on the first and second coordinate derivatives of the scalar order parameters. Our approach is applied to several models of inhomogeneous ionic liquids that consider electrostatic correlations of ions or short-range correlations related to packing effects. Specifically, we derive analytical expressions for the symmetric stress tensors of the Cahn–Hilliard-like model, Bazant–Storey–Kornyshev model, and Maggs–Podgornik–Blossey model. All of these expressions are found to be consistent with respective self-consistent field equations. [ABSTRACT FROM AUTHOR]

In this paper, we present a new module to predict the potential surface reconstruction configurations of given surface structures in the framework of our machine learning and graph theory assisted universal structure searcher. In addition to random structures generated with specific lattice symmetry, we made full use of bulk materials to obtain a better distribution of population energy, namely, randomly appending atoms to a surface cleaved from bulk structures or moving/removing some of the atoms on the surface, which is inspired by natural surface reconstruction processes. In addition, we borrowed ideas from cluster predictions to spread structures better between different compositions, considering that surface models of different atom numbers usually have some building blocks in common. To validate this newly developed module, we tested it with studies on the surface reconstructions of Si (100), Si (111), and 4H–SiC (1 1 ̄ 02) − c (2 × 2) , respectively. We successfully gave the known ground states, as well as a new SiC surface model, in an extremely Si-rich environment. [ABSTRACT FROM AUTHOR]

In this paper, we present dyadic adaptive HOPS (DadHOPS), a new method for calculating linear absorption spectra for large molecular aggregates. This method combines the adaptive HOPS (adHOPS) framework, which uses locality to improve computational scaling, with the dyadic HOPS method previously developed to calculate linear and nonlinear spectroscopic signals. To construct a local representation of dyadic HOPS, we introduce an initial state decomposition that reconstructs the linear absorption spectra from a sum over locally excited initial conditions. We demonstrate the sum over initial conditions can be efficiently Monte Carlo sampled and that the corresponding calculations achieve size-invariant [i.e., O (1) ] scaling for sufficiently large aggregates while trivially incorporating static disorder in the Hamiltonian. We present calculations on the photosystem I core complex to explore the behavior of the initial state decomposition in complex molecular aggregates as well as proof-of-concept DadHOPS calculations on an artificial molecular aggregate inspired by perylene bis-imide to demonstrate the size-invariance of the method. [ABSTRACT FROM AUTHOR]

Semiflexible slender filaments are ubiquitous in nature and cell biology, including in the cytoskeleton, where reorganization of actin filaments allows the cell to move and divide. Most methods for simulating semiflexible inextensible fibers/polymers are based on discrete (bead-link or blob-link) models, which become prohibitively expensive in the slender limit when hydrodynamics is accounted for. In this paper, we develop a novel coarse-grained approach for simulating fluctuating slender filaments with hydrodynamic interactions. Our approach is tailored to relatively stiff fibers whose persistence length is comparable to or larger than their length and is based on three major contributions. First, we discretize the filament centerline using a coarse non-uniform Chebyshev grid, on which we formulate a discrete constrained Gibbs–Boltzmann (GB) equilibrium distribution and overdamped Langevin equation for the evolution of unit-length tangent vectors. Second, we define the hydrodynamic mobility at each point on the filament as an integral of the Rotne–Prager–Yamakawa kernel along the centerline and apply a spectrally accurate "slender-body" quadrature to accurately resolve the hydrodynamics. Third, we propose a novel midpoint temporal integrator, which can correctly capture the Ito drift terms that arise in the overdamped Langevin equation. For two separate examples, we verify that the equilibrium distribution for the Chebyshev grid is a good approximation of the blob-link one and that our temporal integrator for overdamped Langevin dynamics samples the equilibrium GB distribution for sufficiently small time step sizes. We also study the dynamics of relaxation of an initially straight filament and find that as few as 12 Chebyshev nodes provide a good approximation to the dynamics while allowing a time step size two orders of magnitude larger than a resolved blob-link simulation. We conclude by applying our approach to a suspension of cross-linked semiflexible fibers (neglecting hydrodynamic interactions between fibers), where we study how semiflexible fluctuations affect bundling dynamics. We find that semiflexible filaments bundle faster than rigid filaments even when the persistence length is large, but show that semiflexible bending fluctuations only further accelerate agglomeration when the persistence length and fiber length are of the same order. [ABSTRACT FROM AUTHOR]

Second-order N-electron valence state perturbation theory (NEVPT2) is an exactly size-consistent and intruder-state-free multi-reference theory. To accelerate the NEVPT2 computation, Guo and Neese combined it with the local pair-natural orbital (PNO) method using the projected atomic orbitals (PAOs) as the underlying local basis [Guo et al., J. Chem. Phys. 144, 094111 (2016)]. In this paper, we report the further development of the PNO-NEVPT2 method using the orthonormal and non-redundant localized virtual molecular orbitals (LVMOs) instead of PAOs. The LVMOs were previously considered to perform relatively poor compared to PAOs because the resulting orbital domains were unacceptably large. Our prior work, however, showed that this drawback can be remedied by re-forming the domain construction scheme using differential overlap integrals [Saitow et al., J. Chem. Phys. 157, 084101 (2022)]. In this work, we develop further refinements to enhance the feasibility of using LVMOs. We first developed a two-level semi-local approach for screening out so-called weak-pairs to select or truncate the pairs for PNO constructions more flexibly. As a refinement specific to the Pipek–Mezey localization for LVMOs, we introduced an iterative scheme to truncate the Givens rotations using varying thresholds. We assessed the LVMO-based PNO-NEVPT2 method through benchmark calculations for linear phenyl alkanes, which demonstrate that it performs comparably well relative to the PAO-based approach. In addition, we evaluated the Co–C bond dissociation energies for the cobalamin derivatives composed of 200 or more atoms, which confirms that the LVMO-based method can recover more than 99.85% of the canonical NEVPT2 correlation energy. [ABSTRACT FROM AUTHOR]

In two recent papers [A. D. Becke, J. Chem. Phys. 156, 214101 (2022) and A. D. Becke, J. Chem. Phys. 157, 234102 (2022)], we compared two Kohn–Sham density functionals based on physical modeling and theory with the best density-functional power-series fits in the literature. The best error statistics reported to date for a hybrid functional on the general main-group thermochemistry, kinetics, and noncovalent interactions (GMTKN55) chemical database of Goerigk et al. [Phys. Chem. Chem. Phys. 19, 32184 (2017)] were obtained. In the present work, additional second-order perturbation-theory terms are considered. The result is a 12-parameter double-hybrid density functional with the lowest GMTKN55 WTMAD2 "weighted total mean absolute deviation" error (1.76 kcal/mol) yet seen for any hybrid or double-hybrid density-functional approximation. We call it "DH23." [ABSTRACT FROM AUTHOR]

Metal oxide nanoparticle (NP) supports of both good conductivity and stability have the potential to enhance both the reaction activity and stability of the loaded electrocatalysts. In this paper, a facile two-step approach to disperse Pt nanoparticles on the surface of an IrO2 NP support (Pt/IrO2) was developed. Physical characterization by x-ray diffraction spectroscopy and transmission/scanning electron microscopy suggests a good dispersion of the Pt NPs. The temperature effect (from 293 to 353 K) of oxygen reduction reaction on Pt/IrO2 was studied by using a rotating ring disk electrode The results show that although the kinetic current density on Pt/IrO2 is close to that on commercial Pt/C at room temperature, the apparent activation energy (Ea,app) in the former case is much lower, suggesting a much higher activity at elevated temperatures. The superiority in Ea,app is attributed to the electron interaction between Pt and the IrO2 support, as supported by the change of surface chemical state given by x-ray photo-electron spectroscopy. [ABSTRACT FROM AUTHOR]