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Recent 15N R1ρ-relaxation studies have shown that proteins in the solid state undergo slow, low amplitude global motion in the sub-millisecond time range. This range is at the edge of the time window for R1ρ experiments and, therefore, the motional parameters obtained by this method are not precise or reliable. In this paper, we present a 2H stimulated echo study of this type of molecular dynamics. The 2H stimulated echo experiments on a static sample allow for direct measurement of the correlation function in the time range of 10−6–10−1 s, making them well suited to study this type of molecular mobility. We have conducted a detailed analytical and numerical comparison of the correlation functions obtained from the relaxation and stimulated echo experiments, which are generally different. We have identified conditions and algorithms that enable a direct comparison of the relaxation and stimulated echo experimental results. Using the protein GB1 in the form of a lyophilized powder, we have demonstrated that 15N R1ρ-relaxation and 2H stimulated echo experiments yield essentially the same slow-motion correlation function. Surprisingly, this type of motion is observed not only in the protein sample but also in the tripeptide and single amino acid solid samples. The comparison of data measured in these three samples at different temperatures led us to conclude that this slow motion is, in fact, ultrasonic phonons, which seem to be inherent to all rigid biological solids. [ABSTRACT FROM AUTHOR]

In a companion paper, we put forth a thermodynamic model for complex formation via a chemical reaction involving multiple macromolecular species, which may subsequently undergo liquid–liquid phase separation and a further transition into a gel-like state. In the present work, we formulate a thermodynamically consistent kinetic framework to study the interplay between phase separation, chemical reaction, and aging in spatially inhomogeneous macromolecular mixtures. A numerical algorithm is also proposed to simulate domain growth from collisions of liquid and gel domains via passive Brownian motion in both two and three spatial dimensions. Our results show that the coarsening behavior is significantly influenced by the degree of gelation and Brownian motion. The presence of a gel phase inside condensates strongly limits the diffusive transport processes, and Brownian motion coalescence controls the coarsening process in systems with high area/volume fractions of gel-like condensates, leading to the formation of interconnected domains with atypical domain growth rates controlled by size-dependent translational and rotational diffusivities. [ABSTRACT FROM AUTHOR]

Instanton theory relates the rate constant for tunneling through a barrier to the periodic classical trajectory on the upturned potential energy surface, whose period is τ = ℏ/(kBT). Unfortunately, the standard theory is only applicable below the "crossover temperature," where the periodic orbit first appears. This paper presents a rigorous semiclassical (ℏ → 0) theory for the rate that is valid at any temperature. The theory is derived by combining Bleistein's method for generating uniform asymptotic expansions with a real-time modification of Richardson's flux-correlation function derivation of instanton theory. The resulting theory smoothly connects the instanton result at low temperature to the parabolic correction to Eyring transition state theory at high-temperature. Although the derivation involves real time, the final theory only involves imaginary-time (thermal) properties, consistent with the standard version of instanton theory. Therefore, it is no more difficult to compute than the standard theory. The theory is illustrated with application to model systems, where it is shown to give excellent numerical results. Finally, the first-principles approach taken here results in a number of advantages over previous attempts to extend the imaginary free-energy formulation of instanton theory. In addition to producing a theory that is a smooth (continuously differentiable) function of temperature, the derivation also naturally incorporates hyperasymptotic (i.e., multi-orbit) terms and provides a framework for further extensions of the theory. [ABSTRACT FROM AUTHOR]

This paper presents a mean field theory of electrolyte solutions, extending the classical Debye–Hückel–Onsager theory to provide a detailed description of the electrical conductivity in strong electrolyte solutions. The theory systematically incorporates the effects of ion specificity, such as steric interactions, hydration of ions, and their spatial charge distributions, into the mean-field framework. This allows for the calculation of ion mobility and electrical conductivity, while accounting for relaxation and hydrodynamic phenomena. At low concentrations, the model reproduces the well-known Kohlrausch's limiting law. Using the exponential (Slater-type) charge distribution function for solvated ions, we demonstrate that experimental data on the electrical conductivity of aqueous 1:1, 2:1, and 3:1 electrolyte solutions can be approximated over a broad concentration range by adjusting a single free parameter representing the spatial scale of the nonlocal ion charge distribution. Using the fitted value of this parameter at 298.15 K, we obtain good agreement with the available experimental data when calculating electrical conductivity across different temperatures. We also analyze the effects of temperature and electrolyte concentration on the relaxation and electrophoretic contributions to total electrical conductivity, explaining the underlying physical mechanisms responsible for the observed behavior. [ABSTRACT FROM AUTHOR]

Aqueous interfaces containing organic/inorganic molecules are important in various biological, industrial, and atmospheric processes. So far, the study on the dynamics of interfacial molecules has been carried out with time-resolved vibrational sum-frequency generation (TR-VSFG) and time-resolved electronic sum-frequency generation (TR-ESFG) techniques. Although the ESFG probe is powerful for investigating interfacial photochemical dynamics of solute molecules by monitoring the electronic transition of transients or photoproducts at the interface, heterodyne detection is highly desirable for obtaining straightforward information, particularly in time-resolved measurements. So far, heterodyne detection has been realized only for TR-VSFG measurements but not for TR-ESFG measurements. In this paper, we report on femtosecond time-resolved heterodyne-detected ESFG (TR-HD-ESFG) spectroscopy for the first time. With TR-HD-ESFG developed, we measured the time-resolved electronic ΔImχ(2) spectra (pump-induced changes in the imaginary part of the second-order susceptibility) of a prototype dye, malachite green (MG), at the air/water interface. The obtained ΔImχ(2) spectra clearly show not only the ground-state bleach but also the excited-state band of MG at the air/water interface, demonstrating the high potential of TR-HD-ESFG as a new powerful tool to investigate ultrafast reaction dynamics at the interface. [ABSTRACT FROM AUTHOR]

Signaling in cells is full of noise and, hence, described with stochastic biochemical models. Thus, an efficient computation algorithm for these fluctuating reactions is much needed. Apart from the very popular Monte Carlo simulation, methods based on probability distributions are frequently desired due to their analytical tractability and possible numerical advantages in diverse circumstances, among which the variational approach is the most notable. In this paper, new basis functions are proposed to better depict possibly complex distribution profiles, and an extra regularization scheme is supplied to the variational equation to remove occasional degeneracy-induced singularities during the evolution. The new extension is applied to four typical biochemical reaction models and restores the Gillespie results accurately but with greatly reduced simulation time. This modified variational approach is expected to work in a wide range of cell signaling networks. [ABSTRACT FROM AUTHOR]

In 2012, the molecular structure of a new, broad class of ice-binding proteins, classified as "domain of unknown function" (DUF) 3494, was described for the first time. These proteins have a common tertiary structure and are characterized by a very wide spectrum of antifreeze activity (from weakly active to hyperactive). The ice-binding surface (IBS) region of these molecules differs significantly in its structure from the IBS of previously known antifreeze proteins (AFPs), showing a complete lack of regularity and high hydrophilicity. The presence of a regular, repeating structural motif in the IBS region of hitherto known AFP molecules, combined with the hydrophobic nature of this surface, promotes the formation of an ice-like ordering of the solvation water layer and, as a result, facilitates the process of transformation of this water layer into ice. It is, therefore, surprising that the newly discovered DUF3494 class of proteins clearly breaks out of this characteristic. In this paper, using molecular dynamics simulations, we analyze the solvation water structure of the IBS region of both DUF3494 family molecules and AFPs. As we show, although the IBS of DUF3494 molecules does not form an ice-like water structure in the solvation layer, this is compensated by the formation of the equivalent of "anchored clathrate water," in the form of a relatively large number of water molecules bound to the surface of the protein molecule and providing potential binding sites for it to the ice surface. [ABSTRACT FROM AUTHOR]

The generalized quantum master equation (GQME) approach provides a powerful general-purpose framework for simulating the inherently quantum mechanical dynamics of a subset of electronic reduced density matrix elements of interest in complex molecular systems. Previous studies have found that combining the GQME approach with quasiclassical mapping Hamiltonian (QC/MH) methods can dramatically improve the accuracy of electronic populations obtained via those methods. In this paper, we perform a complimentary study of the advantages offered by the GQME approach for simulating the dynamics of electronic coherences, which play a central role in optical spectroscopy, quantum information science, and quantum technology. To this end, we focus on cases where the electronic coherences predicted for the spin-boson benchmark model by direct application of various QC/MH methods are inaccurate. We find that similar to the case of electronic populations, combining the QC/MH methods with the GQME approach can dramatically improve the accuracy of the electronic coherences obtained via those methods. We also provide a comprehensive analysis of how the performance of GQMEs depends on the choice of projection operator and electronic basis and show that the accuracy and feasibility of the GQME approach can benefit from casting the GQME in terms of the eigen-basis of the observable of interest. [ABSTRACT FROM AUTHOR]

ipie is a Python-based auxiliary-field quantum Monte Carlo (AFQMC) package that has undergone substantial improvements since its initial release [Malone et al., J. Chem. Theory Comput. 19(1), 109–121 (2023)]. This paper outlines the improved modularity and new capabilities implemented in ipie. We highlight the ease of incorporating different trial and walker types and the seamless integration of ipie with external libraries. We enable distributed Hamiltonian simulations of large systems that otherwise would not fit on a single central processing unit node or graphics processing unit (GPU) card. This development enabled us to compute the interaction energy of a benzene dimer with 84 electrons and 1512 orbitals with multi-GPUs. Using CUDA and cupy for NVIDIA GPUs, ipie supports GPU-accelerated multi-slater determinant trial wavefunctions [Huang et al. arXiv:2406.08314 (2024)] to enable efficient and highly accurate simulations of large-scale systems. This allows for near-exact ground state energies of multi-reference clusters, [Cu2O2]2+ and [Fe2S2(SCH3)4]2−. We also describe implementations of free projection AFQMC, finite temperature AFQMC, AFQMC for electron–phonon systems, and automatic differentiation in AFQMC for calculating physical properties. These advancements position ipie as a leading platform for AFQMC research in quantum chemistry, facilitating more complex and ambitious computational method development and their applications. [ABSTRACT FROM AUTHOR]

Transport and dispersion of active particles in structured environments, such as corrugated channels and porous media, are important for the understanding of both natural and engineered active systems. Owing to their continuous self-propulsion, active particles exhibit rectified transport under spatially asymmetric confinement. While progress has been made in experiments and particle-based simulations, a theoretical understanding of the effective long-time transport dynamics in spatially periodic geometries remains less developed. In this paper, we apply generalized Taylor dispersion theory to analyze the long-time effective transport dynamics of active Brownian particles (ABPs) in periodic channels and fields. We show that the long-time transport behavior is governed by an effective advection–diffusion equation. The derived macrotransport equations allow us to characterize the average drift and effective dispersion coefficient. For the case of ABPs subject to a no-flux boundary condition at the channel wall, we show that regardless of activity, the average drift is given by the net diffusive flux along the channel. For ABPs, their activity is the driving mechanism that sustains a density gradient, which ultimately leads to rectified motion along the channel. Our continuum theory is validated against direct Brownian dynamics simulations of the Langevin equations governing the motion of each ABP. [ABSTRACT FROM AUTHOR]

The transformative impact of modern computational paradigms and technologies, such as high-performance computing (HPC), quantum computing, and cloud computing, has opened up profound new opportunities for scientific simulations. Scalable computational chemistry is one beneficiary of this technological progress. The main focus of this paper is on the performance of various quantum chemical formulations, ranging from low-order methods to high-accuracy approaches, implemented in different computational chemistry packages and libraries, such as NWChem, NWChemEx, Scalable Predictive Methods for Excitations and Correlated Phenomena, ExaChem, and Fermi–Löwdin orbital self-interaction correction on Azure Quantum Elements, Microsoft's cloud services platform for scientific discovery. We pay particular attention to the intricate workflows for performing complex chemistry simulations, associated data curation, and mechanisms for accuracy assessment, which is demonstrated with the Arrows automated workflow for high throughput simulations. Finally, we provide a perspective on the role of cloud computing in supporting the mission of leadership computational facilities. [ABSTRACT FROM AUTHOR]

A central paradigm of polymer physics states that chains in melts behave like random walks as intra- and interchain interactions effectively cancel each other out. Likewise, θ-chains, i.e., chains at the transition from a swollen coil to a globular phase, are also thought to behave like ideal chains, as attractive forces are counterbalanced by repulsive entropic contributions. While the simple mapping to an equivalent Kuhn chain works rather well in most scenarios with corrections to scaling, random walks do not accurately capture the topology and knots, particularly for flexible chains. In this paper, we demonstrate with Monte Carlo and molecular dynamics simulations that chains in polymer melts and θ-chains not only agree on a structural level for a range of stiffnesses but also topologically. They exhibit similar knotting probabilities and knot sizes, both of which are not captured by ideal chain representations. This discrepancy comes from the suppression of small knots in real chains, which is strongest for very flexible chains because excluded volume effects are still active locally and become weaker with increasing semiflexibility. Our findings suggest that corrections to ideal behavior are indeed similar for the two scenarios of real chains and that the structure and topology of a chain in a melt can be approximately reproduced by a corresponding θ-chain. [ABSTRACT FROM AUTHOR]

This paper investigates the dynamic behavior of EthylChlorophyllide A (EChlideA) molecules in a methanol solution confined within a 4 nm silica nanoslit, using molecular dynamics simulations over a duration of 1 ms. Three systems, containing 1, 2, and 4 solutes, were studied at 298 K. The results demonstrate that EChlideA molecules predominantly adsorb onto the silica surfaces, driven by specific interactions between chlorin ring's methyl group and the hydroxyl groups of the silica. This adsorption leads to stable binding, particularly in less crowded environments, as indicated by the potential of mean force analysis. Higher molecular concentrations, such as those with four EChlideA molecules, introduce variation in binding strength due to molecular aggregation and complex interactions. The orientation analysis reveals that the chlorin ring tends to align parallel to the surface, requiring rotational adjustments during surface diffusion. In addition, solvent coordination around the Mg ion remains consistent under bulk conditions, although with some variation in higher concentrations. This study also highlights a decrease in linear diffusion and an increase in rotational relaxation times for EChlideA molecules within the confined nanoslit, reflecting the influence of molecular concentration and arrangement on their dynamics. These findings provide valuable insights into the role of surface interactions, molecular orientation, and solvent coordination in confined environments, offering implications for the design of nanoscale systems. [ABSTRACT FROM AUTHOR]

An important class of methods for modeling dynamics in open quantum systems is based on the well-known influence functional (IF) approach to solving path-integral equations of motion. Within this paradigm, path-filtering schemes based on the removal of IF elements that fall below a certain threshold aim to reduce the effort needed to calculate and store the influence functional, making very challenging simulations possible. A filtering protocol of this type is considered acceptable as long as the simulation remains mathematically stable. This, however, does not guarantee that the approximated dynamics preserve the physics of the simulated process. In this paper, we explore the possibility of training Generative Flow Networks (GFlowNets) to produce filtering protocols while optimizing for mathematical stability and for physical accuracy. Trained using the trajectory balance objective, the model produces sets of paths to be added to a truncated initial set; it is rewarded if the combined set of paths gives rise to solutions in which the trace of the density matrix is conserved, the populations remain real, and the dynamics approach the exact reference. Using a simple two-level system coupled to a dissipative reservoir, we perform proof-of-concept simulations and demonstrate the elegant and surprising filtering solutions proposed by the GFlowNet. [ABSTRACT FROM AUTHOR]

Action spectroscopies use a readout created by the action of light on the molecules or material rather than optical absorption. Ultrafast 2D photocurrent and 2D fluorescence spectroscopies are two such action spectroscopies. Despite their utility, multidimensional action spectroscopies suffer from a background created by incoherent population mixing. These backgrounds appear when the action of one molecule impacts that of another, creating a signal that mimics a fourth-order population response but is really just the convolution of two linear responses. The background created by incoherent mixing is often much larger than the desired foreground signals. In this paper, we describe the physical mechanisms that give rise to the incoherent signals, drawing Feynman paths for each. There are three variations of incoherent signals, differing by their pulse ordering. They all have the same phase dependence as the desired fourth-order population signals and so cannot be removed by standard phase cycling, but they do differ in their polarization responses and dephasing times. We propose, and implement, a spectrometer design that eliminates the background signals for isotropically oriented samples, leaving only the desired fourth-order 2D action spectra. Our spectrometer utilizes a TWINS interferometer and a pulse shaper interferometer, each driven with a different white-light source so that the pulse pairs within each interferometer are phase stable, but not between the two. The lack of phase stability between the two interferometers eliminates two of the three incoherent responses. The third incoherent response is eliminated with the polarization scheme ⟨0, π/2, π/4, π/4⟩. Our spectrometer also enables both 2D photocurrent and 2D white-light spectra to be collected simultaneously, thereby enabling a direct comparison between action and optical detection under identical conditions and at the exact same position on the sample. Using this spectrometer and photovoltaic devices made from thin films of semiconducting carbon nanotubes, we demonstrate 2D photocurrent spectra free of incoherent background. [ABSTRACT FROM AUTHOR]

The first-principles quantum chemical computations often scale as Nk (N = basis sets; k = 1–4 for linear scaling, Hartree–Fock or density functional theory methods), which makes the development of accurate pseudopotentials and efficient basis sets necessary ingredients in modeling of heavy elements such as lanthanides and actinides. Recently, we have developed 4f-in-core norm-conserving pseudopotentials and associated basis sets for the trivalent lanthanides [Lu et al., J. Chem. Theory Comput. 19, 82–96 (2023)]. In the present paper, we present a unified approach to optimize high-quality Gaussian basis sets for modeling and simulations of condensed-phase systems. The newly generated basis sets not only capture the low total energy and fairly reasonable condition number of overlap matrix of lanthanide-containing systems, but also exhibit good transferability and reproducibility. These advantages ensure the accuracy of the basis sets while avoiding linear dependency concern of atom-centered basis sets. The performance of the basis sets is further illustrated in lanthanide molecular and condensed-phase systems by using Gaussian-plane wave density functional approach of CP2K. These new basis sets can be of particular interest to model structurally complicated lanthanide molecules, clusters, solutions, and solid systems. [ABSTRACT FROM AUTHOR]

The homogeneous electron gas is a system that has many applications in chemistry and physics. However, its infinite nature makes studies at the many-body level complicated due to long computational run times. Because it is size extensive, coupled cluster theory is capable of studying the homogeneous electron gas, but it still poses a large computational challenge as the time needed for precise calculations increases in a polynomial manner with the number of particles and single-particle states. Consequently, achieving convergence in energy calculations becomes challenging, if not prohibited, due to long computational run times and high computational resource requirements. This paper develops the sequential regression extrapolation (SRE) to predict the coupled cluster energies of the homogeneous electron gas in the complete basis limit using Bayesian ridge regression and many-body perturbation theory correlation energies to the second order to make predictions from calculations at truncated basis sizes. Using the SRE method, we were able to predict the coupled cluster double energies for the electron gas across a variety of values of N and rs, for a total of 70 predictions, with an average error of 5.20 × 10−4 hartree while saving 88.9 h of computational time. The SRE method can accurately extrapolate electron gas energies to the complete basis limit, saving both computational time and resources. Additionally, the SRE is a general method that can be applied to a variety of systems, many-body methods, and extrapolations. [ABSTRACT FROM AUTHOR]

The Atomic, Molecular, and Optical Science (AMOS) Gateway is a comprehensive cyberinfrastructure for research and educational activities in computational AMO science. The B-Spline atomic R-Matrix (BSR) suite of programs is one of several computer programs currently available on the gateway. It is an excellent example of the gateway's potential to increase the scientific productivity of AMOS users. While the suite is available to be used in batch mode, its complexity does not make it well-suited to the approach taken in the gateway's default setup. The complexity originates from the need to execute many different computations and to construct generally complex workflows, requiring numerous input files that must be used in a specific sequence. The BSR graphical user interface described in this paper was developed to considerably simplify employing the BSR codes on the gateway, making BSR available to a large group of researchers and students interested in AMO science. [ABSTRACT FROM AUTHOR]

In molecular physics, it is often necessary to average over the orientation of molecules when calculating observables, in particular when modeling experiments in the liquid or gas phase. Evaluated in terms of Euler angles, this is closely related to integration over two- or three-dimensional unit spheres, a common problem discussed in numerical analysis. The computational cost of the integration depends significantly on the quadrature method, making the selection of an appropriate method crucial for the feasibility of simulations. After reviewing several classes of spherical quadrature methods in terms of their efficiency and error distribution, we derive guidelines for choosing the best quadrature method for orientation averages and illustrate these with three examples from chiral molecule physics. While Gauss quadratures allow for achieving numerically exact integration for a wide range of applications, other methods offer advantages in specific circumstances. Our guidelines can also be applied to higher-dimensional spherical domains and other geometries. We also present a Python package providing a flexible interface to a variety of quadrature methods. [ABSTRACT FROM AUTHOR]

In a well-known paper, Jeremy England derived a bound on the free energy dissipated by a self-replicating system [J. L. England, "Statistical physics of self-replication," J. Chem. Phys. 139, 121923 (2013)]. This bound is usually interpreted as a universal relationship that connects thermodynamic dissipation to replicator per-capita decay and growth rates. We argue from basic thermodynamic principles against this interpretation. In fact, we suggest that such a relationship cannot exist in principle, because it is impossible for a thermodynamically consistent replicator to undergo both per-capita growth and per-capita decay back into reactants. Instead, replicator may decay into separate waste products, but in that case, replication and decay are two independent physical processes, and there is no universal relationship that connects their thermodynamic and dynamical properties. [ABSTRACT FROM AUTHOR]

Designing coatings and films that can protect surfaces is important in a wide variety of applications from corrosion prevention to anti-fouling. These systems are challenging from a modeling perspective because they are invariably multicomponent, which quickly leads to an expansive design space. At a minimum, the system has a substrate, a film (often composed of a polymeric material), a ubiquitous carrier solvent, which may be either a vapor or liquid phase, and one or more contaminants. Each component has an impact on the effectiveness of coating. This paper focuses on films that are used as a barrier to surface contamination, but the results also extend to surface coatings that are designed to extract a low density species from the fluid phase as in liquid chromatography. A coarse-grained model is developed using Yukawa potentials that encompasses both repulsive and attractive interactions among the species. Classical density functional theory calculations are presented to show how contaminant adsorption is controlled by the molecular forces in the system. Two specific vectors through the parameter space are considered to address likely experimental manipulations that change either the solvent or the polymer in a system. We find that all the adsorption results can be unified by considering an appropriate combination of molecular parameters. As a result, these calculations provide a link between molecular interactions and film performance and may serve to guide the rational design of films. [ABSTRACT FROM AUTHOR]

Heterojunction catalysts in the field of hydrogen evolution reaction (HER) from electrocatalytic water splitting have recently become a hot research topic. In this paper, we systematically calculated the HER catalytic performance of a MoS2/CoS2 heterojunction for the first time, considering the effect of edge sites regulation, strain and electric field. The results indicate that the MoS2/CoS2 heterojunction exhibits synergistic catalytic performance compared to MoS2 and CoS2, the HER catalytic activity of which can be improved by exposing more edge sites or regulating the S content on the edges, with an optimized ratio of 25%. Surprisingly, applying strain has a slight effect on the catalytic activity of the edge, however, an obvious effect on the basal plane. For example, applying 2% tensile strain on the MoS2/CoS2 heterojunction can improve the edge catalytic performance by 13%, and for the basal plane, this value can reach 92%. In this case, the catalytic performance of the basal plane is better than that of the edge with 2% and without strain. Since the basal plane accounts for the majority of the two-dimensional catalysts, the catalytic performance of the basal plane is generally much lower than that of the edge. This discovery is of great significance, which means by adjusting strain, the catalytic performance of the heterojunction catalyst is likely to be improved by orders of magnitude. Moreover, considering the actual experimental process, we also calculated the effect of the electric field and found that 0.7 V/Å electric field can enhance the HER catalytic activity of the MoS2/CoS2 heterojunction by 23%. [ABSTRACT FROM AUTHOR]

The calculation of molecular excited states is critically important to decipher a plethora of molecular properties. In this paper, we develop an equation of motion formalism on top of a bi-exponentially parameterized ground state wavefunction toward the determination of excited states. While the ground state bi-exponential parameterization ensures an accurate description of the wavefunction through the inclusion of high-rank correlation effects, the excited state is parameterized by a novel linear response operator with an effective excitation rank beyond two. To treat the ground and excited states in the same footings, in addition to the conventional one- and two-body response operators, we introduced certain two-body "generalized" response operators with an effective excitation rank of one. We introduce a projective formulation for determining the perturbed amplitudes for the set of "generalized" operators. Our formulation entails a significantly small number of unknown parameters and is shown to be highly accurate compared to allied methods for several difficult chemical systems. [ABSTRACT FROM AUTHOR]

Liquid–liquid phase transitions hold a unique and profound significance within condensed matter physics. These transitions, while conceptually intriguing, often pose formidable computational challenges. However, recent advances in neural network (NN) potentials offer a promising avenue to effectively address these challenges. In this paper, we delve into the structural transitions of liquid CdTe, CdS, and their alloy systems using molecular dynamics simulations, harnessing the power of an NN potential named LaspNN. Our investigations encompass both pressure and temperature effects. Through our simulations, we uncover three primary liquid structures around melting points that emerge as pressure increases: tetrahedral, rock salt, and close-packed structures, which greatly resemble those of solid states. In the high-temperature regime, we observe the formation of Te chains and S dimers, providing a deeper understanding of the liquid's atomic arrangements. When examining CdSxTe1−x alloys, our findings indicate that a small substitution of S by Te atoms for S-rich alloys (x > 0.5) exhibits a structural transition much different from CdS, while a large substitution of Te by S atoms for Te-rich alloys (x < 0.5) barely exhibits a structural transition similar to CdTe. We construct a schematic diagram for liquid alloys that considers both temperature and pressure, providing a comprehensive overview of the alloy system's behavior. The local aggregation of Te atoms demonstrates a linear relationship with alloy composition x, whereas that of S atoms exhibits a nonlinear one, shedding light on the composition-dependent structural changes. [ABSTRACT FROM AUTHOR]

In this paper, we investigate the Feshbach resonances of high partial waves and the influence of spin–spin (S–S) interaction on ultracold scattering processes. Taking the N a 23 - R b 87 system as an example, we plot the variations of weakly bound state energy and elastic scattering cross section with magnetic field and with collision energy. We find that the number of splittings in high partial wave Feshbach resonances does not strictly conform to the expected l + 1 (l is rotational angular momentum), and the deviation is attributed to the influence of bound states in other channels coupled by S–S interaction. For different ml (the projection of l on the external magnetic field direction), the effects of S–S interaction lead to different scattering patterns in the incident channels. These results reveal the complex features of ultracold scattering processes in high partial waves caused by S–S interaction. [ABSTRACT FROM AUTHOR]

Strong light–matter coupling within an optical cavity leverages the collective interactions of molecules and confined electromagnetic fields, giving rise to the possibilities of modifying chemical reactivity and molecular properties. While collective optical responses, such as enhanced Rabi splitting, are often observed, the overall effect of the cavity on molecular systems remains ambiguous for a large number of molecules. In this paper, we investigate the non-adiabatic electron transfer process in electron donor–acceptor pairs influenced by collective excitation and local molecular dynamics. Using the timescale difference between reorganization and thermal fluctuations, we derive analytical formulas for the electron transfer rate constant and the polariton relaxation rate. These formulas apply to any number of molecules (N) and account for the collective effect as induced by cavity photon coupling. Our findings reveal a non-monotonic dependence of the rate constant on N, which can be understood by the interplay between electron transfer and polariton relaxation. As a result, the cavity-induced quantum yield increases linearly with N for small N (as predicted by a simple Dicke model) but shows a turnover and suppression for large N. We also interrelate the thermal bath frequency and the number of molecules, suggesting the optimal number for maximizing enhancement. The analysis provides an analytical insight for understanding the collective excitation of light and electron transfer, helping to predict the optimal condition for effective cavity-controlled chemical reactivity. [ABSTRACT FROM AUTHOR]

Understanding how external electric fields (EFs) impact the properties of aqueous molecules is crucial for various applications in chemistry, biology, and engineering. In this paper, we present a study utilizing molecular dynamics simulation to explore how direct-current (DC) and alternative-current (AC) EFs affect hydrophobic (n-triacontane) and hydrophilic (PEG-10) oligomer chains. Through a machine learning approach, we extract a 2-dimensional free energy (FE) landscape of these molecules, revealing that electric fields modulate the FE landscape to favor stretched configurations and enhance the alignment of the chain with the electric field. Our observations indicate that DC EFs have a more prominent impact on modulation compared to AC EFs and that EFs have a stronger effect on hydrophobic chains than on hydrophilic oligomers. We analyze the orientation of water dipole moments and hydrogen bonds, finding that EFs align water molecules and induce more directional hydrogen bond networks, forming 1D water structures. This favors the stretched configuration and alignment of the studied oligomers simultaneously, as it minimizes the disruption of 1D structures. This research deepens our understanding of the mechanisms by which electric fields modulate molecular properties and could guide the broader application of EFs to control other aqueous molecules, such as proteins or biomolecules. [ABSTRACT FROM AUTHOR]

This second paper in a series of two describes the chirped-pulse ice apparatus that permits the detection of buffer gas cooled molecules desorbed from an energetically processed ice using broadband mm-wave rotational spectroscopy. Here, we detail the lower ice stage developed to generate ices at 4 K, which can then undergo energetic processing via UV/VUV photons or high-energy electrons and which ultimately enter the gas phase via temperature-programmed desorption (TPD). Over the course of TPD, the lower ice stage is interfaced with a buffer gas cooling cell that allows for sensitive detection via chirped-pulse rotational spectroscopy in the 60–90 GHz regime. In addition to a detailed description of the ice component of this apparatus, we show proof-of-principle experiments demonstrating the detection of H2CO products formed through irradiation of neat methanol ices or 1:1 CO + CH4 mixed ices. [ABSTRACT FROM AUTHOR]

The high resolution Rydberg absorption spectrum of 2-butyne C4H6 recorded previously at the SOLEIL synchrotron facility has been interpreted using multichannel quantum defect theory (MQDT). The calculations are based on the continuum scattering calculations of Xu et al., J. Chem. Phys. 136, 154303 (2012) and of Jacovella et al., J. Phys. Chem. A 119, 12339 (2015) pertaining to the dipole-allowed excited state symmetries in absorption from the ground state. In contrast to the traditional approach of calculating low-lying electronic states first and then attempting to extend the calculations to ever higher energy, here the analysis proceeds through the extension of these detailed calculations of the electronic continuum scattering down into the discrete region of the spectrum. The continuum reaction matrices and dipole transition moments are adapted to the discrete Rydberg region via the use of an energy-modified formulation of MQDT theory and associated energy dependences of the quantum defects. The analysis reproduces more than 40 Rydberg states from n ≈ 10 down to the 3d and 4s levels with an rms error of better than 20 cm−1. These belong to five Rydberg series with three different molecular symmetries. While the approach predicts many additional series, most of these are calculated and observed to carry only little oscillator strength. The analysis shows that the Rydberg spectrum is dominated by the excitation of an e″ symmetry electron of fδ and gπ type, in line with what previous studies of the above-threshold shape resonance of 2-butyne have shown. The present study is intended to serve as an example showing how first principles continuum calculations may be useful for the interpretation of highly bound discrete states in a range that poses problems for the standard ab initio techniques. The quantitative treatment of the dipole absorption cross sections is deferred to a future paper. [ABSTRACT FROM AUTHOR]

Presents a response to the commentary on the article 'Further Contributions to the Energy Levels of a Perturbed Anharmonic Oscillator: Application to Adiabatic Corrections.'

An error in the theoretical treatment by Hadinger et al., using the experimental data on HCl of Coxon and Ogilvie, is pointed out. [ABSTRACT FROM AUTHOR]

In Paper I, the performances of pre-screening (PS), extended PS (EPS), and cumulant (CU) approximations to the fourth-order density matrix were examined in the context of second-order N-electron valence state perturbation theory (NEVPT2). It has been found that the CU, PS, and even EPS approximations with loose thresholds may introduce intruder states. In the present work, the origin of these "false intruder" states introduced by approximated density matrices is discussed. Canonical NEVPT2 implementations employ a rank reduction trick. By analyzing its residual error, we find that the omission of the rank reduction leads to a more stable multireference perturbation theory for incomplete active space reference wave functions. Such a full rank (FR)-NEVPT2 formulation is equivalent to the conventional NEVPT2 method for the complete active space self-consistent field/complete active space configuration interaction reference wave function. A major drawback of the FR-NEVPT2 formulation is the necessity of the fifth-order density matrix. To avoid the construction of the high-order density matrices, the combination of the FR-NEVPT2 with the CU approximation is studied. However, we find that the CU approximation remains problematic as it still introduces intruder states. The question of how to robustly and efficiently perform internally contracted multireference perturbation theories with approximate densities remains a challenging field of investigation. [ABSTRACT FROM AUTHOR]

This paper proposes the first linear scaling implementation for the domain decomposition approach of the polarizable continuum model (ddPCM) for the computation of the solvation energy and forces. The ddPCM-equation consists of a (non-local) integral equation on the van der Waals or solvent accessible surface of the solute's cavity resulting in a dense solution matrix, and, in turn, one matrix–vector multiplication has a quadratic arithmetic complexity with respect to the number of atoms of the solute molecule. The use of spherical harmonics as basis functions makes it natural to employ the fast multipole method (FMM) in order to provide an asymptotically linear scaling method. In this paper, we employ the FMM in a non-uniform manner with a clusterization based on a recursive inertial bisection. We present some numerical tests illustrating the accuracy and scaling of our implementation. [ABSTRACT FROM AUTHOR]

The Modified Genetic Algorithm scheme, presented in Paper I to model crystal structures in organic compounds (MGAC), is applied here to test its performance in the determination of a polymorphic crystalline structure of benzene that has been observed at 25 Kbar. This polymorph, named here benzene II, is not a global minimum of the energy or even close to any of the local minimum determined using the energy evolution of benzene structures described in the previous paper. The benzene II structure corresponds to an enthalpy minimum. This paper shows that it is possible to use the MGAC procedure, modified to use the minimization of the enthalpy instead of the energy in the GA (Genetic Algorithm) selection process, to find this high pressure structure of benzene. [ABSTRACT FROM AUTHOR]

Results on single-wavelength transient hole burning (SW-THB) developed in paper II [J. Chem. Phys. 115, 4223 (2001)] are applied to the dichroism experiments on anthracene in benzyl alcohol reported in paper I [J. Chem. Phys. 115, 4212 (2001)]. The intermediate component of the dichroism decay is assigned to a SW-THB effect caused by nonpolar electronic solvation. The presence of a solvation component in dichroism experiments has not been demonstrated previously. The sparseness of anthracene’s electronic spectrum eliminates vibrational dynamics from the solvation measurement. Because data collection is focused on a single dimension, the viscosity dependence of the nonpolar solvation is determined with greater accuracy than in our previous two-dimensional transient hole-burning studies. The solvation time is obtained as a function of viscosity/temperature from 14.4 to 2.7 cP (1–56 °C). The times show good agreement with a viscoelastic theory of the diffusive component of nonpolar solvation. Combining the results of this paper with those of paper I allows for comparison of solvation and rotation dynamics within a single system. A correlation between the ratio of diffusive solvation and rotation times and the magnitude of the inertial rotation is suggested. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Experimental demonstrations of polarization-selection two-dimensional Vibrational-Electronic (2D VE) and 2D Electronic-Vibrational (2D EV) spectroscopies aim to map the magnitudes and spatial orientations of coupled electronic and vibrational coordinates in complex systems. The realization of that goal depends on our ability to connect spectroscopic observables with molecular structural parameters. In this paper, we use a model Hamiltonian consisting of two anharmonically coupled vibrational modes in electronic ground and excited states with linear and bilinear vibronic coupling terms to simulate polarization-selective 2D EV and 2D VE spectra. We discuss the relationships between the linear vibronic coupling and two-dimensional Huang–Rhys parameters and between the bilinear vibronic coupling term and Duschinsky mixing. We develop a description of the vibronic transition dipoles and explore how the Hamiltonian parameters and non-Condon effects impact their amplitudes and orientations. Using simulated polarization-selective 2D EV and 2D VE spectra, we show how 2D peak positions, amplitudes, and anisotropy can be used to measure parameters of the vibronic Hamiltonian and non-Condon effects. This paper, along with the first in the series, provides the reader with a detailed description of reading, simulating, and analyzing multimode, polarization-selective 2D EV and 2D VE spectra with an emphasis on extracting vibronic coupling parameters from complex spectra. [ABSTRACT FROM AUTHOR]

Two-dimensional Electronic–Vibrational (2D EV) spectroscopy and two-dimensional Vibrational–Electronic (2D VE) spectroscopy are among the newest additions to the coherent multidimensional spectroscopy toolbox, and they are directly sensitive to vibronic couplings. In this first of two papers, the complete orientational response functions are developed for a model system consisting of two coupled anharmonic oscillators and two electronic states in order to simulate polarization-selective 2D EV and 2D VE spectra with arbitrary combinations of linearly polarized electric fields. Here, we propose analytical methods to isolate desired signals within complicated spectra and to extract the relative orientation between vibrational and vibronic dipole moments of the model system using combinations of polarization-selective 2D EV and 2D VE spectral features. Time-dependent peak amplitudes of coherence peaks are also discussed as means for isolating desired signals within the time-domain. This paper serves as a field guide for using polarization-selective 2D EV and 2D VE spectroscopies to map coupled vibronic coordinates on the molecular frame. [ABSTRACT FROM AUTHOR]

The objective of this paper is to describe a new data-driven framework for computational screening and discovery of a class of materials termed "metavalent" solids. "Metavalent" solids possess characteristics that are nominally associated with metallic and covalent bonding (in terms of conductivity and coordination numbers) but are distinctly different from both because they show anomalously large response properties and a unique bond-breaking mechanism that is not observed in either covalent or metallic solids. The paper introduces the use of Hirshfeld surface analysis to provide quantum level descriptors that can be used for rapid screening of crystallographic data to identify potentially new "metavalent" solids with novel and emergent properties. [ABSTRACT FROM AUTHOR]

Stable crystalline structures of confined water can be different from bulk ice. In Paper I [T. Yagasaki et al., J. Chem. Phys. 151, 064702 (2019)] of this study, it was shown, using molecular dynamics (MD) simulations, that a zeolite-like ice structure forms in nanobrushes consisting of (6,6) carbon nanotubes (CNTs) when the CNTs are located in a triangle arrangement. The melting temperature of the zeolite-like ice structure is much higher than the melting temperature of ice Ih when the distance between the surfaces of CNTs is ∼0.94 nm, which is the best spacing for the bilayer structure of water. In this paper, we perform MD simulations of nanobrushes of CNTs that are different from (6,6) CNTs in radius. Several new porous ice structures form spontaneously in the MD simulations. A stable porous ice forms when the radius of its cavities matches the radius of the CNTs well. All cylindrical porous ice structures found in this study can be decomposed into a small number of structural blocks. We provide a new protocol to classify cylindrical porous ice crystals on the basis of this decomposition. [ABSTRACT FROM AUTHOR]

Two-dimensional transition metal dichalcogenides and semiconductor metal oxides have shown great potential in photocatalysis. However, their stability and efficiency need to be further improved. In this paper, porous ZnO nanorods with high specific surface area were prepared from metal-organic framework ZIF-8 by a simple hydrothermal method. A MoS2/ZnO composite was constructed by loading MoS2 onto the surface of porous ZnO nanorods. Compared with ZnO materials prepared by other methods, MoS2/ZnO prepared in this paper exhibits superior photocatalytic performance. The enhanced photocatalytic activity of the MoS2/ZnO composite can be attributed to the formation of heterojunctions and strong interaction between them, which greatly facilitate the separation of electrons and holes at the contact interface. In addition, due to the wide absorption region of the visible spectrum, MoS2 can greatly broaden the light absorption range of the material after the formation of the composite material, increase the utilization rate of visible light, and reduce the combination of electrons and holes. This study provides a new way to prepare cheap and efficient photocatalysts. [ABSTRACT FROM AUTHOR]

Developing fluorescence-encoded infrared (FEIR) vibrational spectroscopy for single-molecule applications requires a detailed understanding of how the molecular response and external experimental parameters manifest in the detected signals. In Paper I [L. Whaley-Mayda, A. Guha, and A. Tokmakoff, J. Chem. Phys. 159, 194201 (2023)] we introduced a nonlinear response function theory to describe vibrational dynamics, vibronic coupling, and transition dipole orientation in FEIR experiments with ultrashort pulses. In this second paper, we apply the theory to investigate the role of intermode vibrational coherence, the orientation of vibrational and electronic transition dipoles, and the effects of finite pulse durations in experimental measurements. We focus on measurements at early encoding delays—where signal sizes are largest and therefore of most value for single-molecule experiments, but where many of these phenomena are most pronounced and can complicate the appearance of data. We compare experiments on coumarin dyes with finite-pulse response function simulations to explain the time-dependent behavior of FEIR spectra. The role of the orientational response is explored by analyzing polarization-dependent experiments and their ability to resolve relative dipole angles in the molecular frame. This work serves to demonstrate the molecular information content of FEIR experiments, and develop insight and guidelines for their interpretation. [ABSTRACT FROM AUTHOR]

Fluorescence-encoded infrared (FEIR) spectroscopy is an emerging technique for performing vibrational spectroscopy in solution with detection sensitivity down to single molecules. FEIR experiments use ultrashort pulses to excite a fluorescent molecule's vibrational and electronic transitions in a sequential, time-resolved manner, and are therefore sensitive to intervening vibrational dynamics on the ground state, vibronic coupling, and the relative orientation of vibrational and electronic transition dipole moments. This series of papers presents a theoretical treatment of FEIR spectroscopy that describes these phenomena and examines their manifestation in experimental data. This first paper develops a nonlinear response function description of Fourier-transform FEIR experiments for a two-level electronic system coupled to multiple vibrations, which is then applied to interpret experimental measurements in the second paper [L. Whaley-Mayda et al., J. Chem. Phys. 159, 194202 (2023)]. Vibrational coherence between pairs of modes produce oscillatory features that interfere with the vibrations' population response in a manner dependent on the relative signs of their respective Franck–Condon wavefunction overlaps, leading to time-dependent distortions in FEIR spectra. The orientational response of population and coherence contributions are analyzed and the ability of polarization-dependent experiments to extract relative transition dipole angles is discussed. Overall, this work presents a framework for understanding the full spectroscopic information content of FEIR measurements to aid data interpretation and inform optimal experimental design. [ABSTRACT FROM AUTHOR]

Effect mechanisms of the undercooling degree and the surface configuration on the ice growth characteristics were revealed under micro-droplets icing conditions. Preferential ice crystals appear firstly on the surfaces due to the randomness of icing, and obtain growth advantages to form protruding structures. Protruding structures block the incoming droplets from contacting the substrates, causing voids around the structures. The undercooling degree mainly affects the density and the growth rate of preferential ice crystals. With the increase of undercooling degree, the preferential ice crystals have higher density and growth rate, resulting in stronger growth advantage and higher porosity. The surface configuration affects the growth mode, and the ice layer grows with uniform mode, spreading mode and structure-induced mode on the aluminum, smooth Polytetrafluoroethylene (PTFE) and rough PTFE surface respectively, causing the needle-like, ridge-like and cluster-like ice crystals. The rough structures effectively improve the porosity of the ice layer, which is beneficial for optimizing the icephobic property of the materials. This paper provides important theoretical guidance for the design of subsequent icephobic materials. [ABSTRACT FROM AUTHOR]

Computing the solubility of crystals in a solvent using atomistic simulations is notoriously challenging due to the complexities and convergence issues associated with free-energy methods, as well as the slow equilibration in direct-coexistence simulations. This paper introduces a molecular-dynamics workflow that simplifies and robustly computes the solubility of molecular or ionic crystals. This method is considerably more straightforward than the state-of-the-art, as we have streamlined and optimised each step of the process. Specifically, we calculate the chemical potential of the crystal using the gas-phase molecule as a reference state, and employ the S0 method to determine the concentration dependence of the chemical potential of the solute. We use this workflow to predict the solubilities of sodium chloride in water, urea polymorphs in water, and paracetamol polymorphs in both water and ethanol. Our findings indicate that the predicted solubility is sensitive to the chosen potential energy surface. Furthermore, we note that the harmonic approximation often fails for both molecular crystals and gas molecules at or above room temperature, and that the assumption of an ideal solution becomes less valid for highly soluble substances. [ABSTRACT FROM AUTHOR]

Quantitative descriptions of non-adiabatic transition rates at intermediate temperatures are challenging due to the simultaneous importance of quantum and anharmonic effects. In this paper, the interplay between quantum effects—for motion across or along the seam of crossing—and anharmonicity in the seam potential is considered within the weak coupling limit. The well-known expression for quantized 1-D motion across the seam (i.e., tunneling) in the linear terms approximation is derived in the thermal domain using the Lagrangian formalism, which is then applied to the case when tunneling is distributed along the seam of crossing (treating motion along the seam classically). For high-frequency quantum modes, a vibrationally adiabatic (VA) approach is developed that introduces to the non-adiabatic rate constant a factor associated with high-frequency wavefunction overlap; this approach treats the high-frequency motion along the seam quantum mechanically. To test these methodologies, the reaction N2O ↔ N2 + O(3P) was chosen. CCSD(T)-F12b/cc-pVTZ-F12 explorations of the 3A′-1A′ seam of N2O revealed that seam anharmonicity has a strong effect on the rate constant (a factor of ∼ 20 at 2000 K). Several quantum effects were found to be significant at intermediate/lower temperatures, including the quantum N–N vibration that was coupled with seam anharmonicity using the VA approach. Finally, a 1-D approximation to non-adiabatic instanton theory is presented to estimate the validity limit of the linear terms model at low temperatures (∼ 250 K for N2O). We recommend that the assumptions built into many statistical theories for non-adiabatic reactions—harmonic behavior, classical motion, linear terms, and weak coupling—should be verified on a case-by-case basis. [ABSTRACT FROM AUTHOR]

The exponential-6 (exp-6) potential is commonly used to model fluids at high densities. In this paper, I propose a new equation of state (EOS) in the form of an analytical expression for the excess Helmholtz free energy of an exp-6 fluid. The EOS is based on extensive Monte Carlo simulations and therefore combines the excellent accuracy of the simulations with the numerical efficiency of a polynomial expression. The mean relative error in compressibility factor and internal energy is 0.14% and 0.25% respectively, which is a significant improvement over statistical mechanical theories. The EOS was implemented into a thermochemical code in order to optimize gas parameters and evaluate its performance on pure gas data, shock compression and detonation properties. Predicted gas densities, heat capacities and speed of sound for pure gases were generally within experimental uncertainties at pressures up to 1 GPa and temperatures above 300 K. For polar molecules, a simple free energy correction was introduced which greatly improved accuracy at low temperature. Calculated shock Hugoniots showed excellent agreement with experimental values up to 150 GPa and 10 000 K, and the detonation performance was accurately predicted for a number of different types of explosives. [ABSTRACT FROM AUTHOR]

In this paper we establish a connection between density functional theory (DFT) for lattice models and common real-space DFT. We consider the lattice DFT description of a two-level model subject to generic interactions in Mermin's DFT formulation in the grand canonical ensemble at finite temperature. The case of only density–density and Hund's rule interaction studied in earlier work is shown to be equivalent to an exact-exchange description of DFT in the real-space picture. In addition, we also include the so-called pair-hopping interaction which can be treated analytically and, crucially, leads to non-integer occupations of the Kohn–Sham (KS) levels even in the limit of zero temperature. Treating the hydrogen molecule in a minimal basis is shown to be equivalent to our two-level lattice DFT model. By means of the fractional occupations of the KS orbitals (which, in this case, are identical to the many-body ones) we reproduce the results of full configuration interaction, even in the dissociation limit and without breaking the spin symmetry. Beyond the minimal basis, we embed our HOMO-LUMO model into a standard DFT calculation and, again, obtain results in overall good agreement with exact ones without the need of breaking the spin symmetry. [ABSTRACT FROM AUTHOR]

Kinetic theory has long predicted that temperature inversion may happen in the vapor-phase for evaporation and condensation between two parallel plates, i.e., the vapor temperature at the condensation interface is higher than that at the evaporation interface. However, past studies have neglected transport in the liquid phases, which usually determine the evaporation and condensation rates. This disconnect has limited the acceptance of the kinetic theory in practical heat transfer models. In this paper, we combine interfacial conditions for mass and heat fluxes with continuum descriptions in the bulk regions of the vapor and the liquid phases to obtain a complete picture for the classical problem of evaporation and condensation between two parallel plates. The criterion for temperature inversion is rederived analytically. We also prove that the temperature jump at each interface is in the same direction as externally applied temperature difference, i.e., liquid surface is at a higher temperature than its adjacent vapor on the evaporating interface and at a lower temperature than its adjacent vapor on the condensing interface. We explain the interfacial temperature jump and temperature inversion using the interfacial cooling and heating processes, and we predict that this process can lead to a vapor phase temperature much lower than the lowest wall temperatures and much higher than the highest wall temperature imposed. When the latent heat of evaporation is small, we found that evaporation can happen at the low temperature side while condensation occurs at the high temperature side, opposing the temperature gradient. [ABSTRACT FROM AUTHOR]

Modeling the dynamics of glassy systems has been challenging in physics for several decades. Recent studies have shown the efficacy of Graph Neural Networks (GNNs) in capturing particle dynamics from the graph structure of glassy systems. However, current GNN methods do not take the dynamic patterns established by neighboring particles explicitly into account. In contrast to these approaches, this paper introduces a novel dynamical parameter termed "smoothness" based on the theory of graph signal processing, which explores the dynamic patterns from a graph perspective. Present graph-based approaches encode structural features without considering smoothness constraints, leading to a weakened correlation between structure and dynamics, particularly on short timescales. To address this limitation, we propose a Geometry-enhanced Graph Neural Network (Geo-GNN) to learn the smoothness of dynamics. Results demonstrate that our method outperforms state-of-the-art baselines in predicting glassy dynamics. Ablation studies validate the effectiveness of each proposed component in capturing smoothness within dynamics. These findings contribute to a deeper understanding of the interplay between glassy dynamics and static structure. [ABSTRACT FROM AUTHOR]