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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]

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]

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]

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]

We report further investigations to aid the development of a Laplace MP2 (second-order Møller Plesset) method with a range separated Coulomb potential partitioned into short- and long-range parts. The implementation of the method extensively uses sparse matrix algebra, density fitting techniques for the short-range part, and a Fourier transformation in spherical coordinates for the long-range part of the potential. Localized molecular orbitals are employed for the occupied space, whereas virtual space is described by orbital specific virtual orbitals (OSVs) associated with localized molecular orbitals. The Fourier transform is deficient for very large distances between localized occupied orbitals, and a multipole expansion for widely separated pairs is introduced for the direct MP2 contribution, which is applicable also to non-Coulombic potentials that do not satisfy the Laplace equation. For the exchange contribution, an efficient screening of contributing localized occupied pairs is employed, which is discussed more completely here. To mitigate errors due to the truncation of OSVs, a simple and efficient extrapolation procedure is used to obtain results close to MP2 for the full basis set of atomic orbitals Using a suitable set of default parameters, the accuracy of the approach is demonstrated. The current implementation of the approach is not very efficient, and the aim of this paper is to introduce and critically discuss ideas that can have more general applicability beyond MP2 calculations for large molecules. [ABSTRACT FROM AUTHOR]

The complexity of mathematical models in biology has rendered model reduction an essential tool in the quantitative biologist's toolkit. For stochastic reaction networks described using the Chemical Master Equation, commonly used methods include time-scale separation, Linear Mapping Approximation, and state-space lumping. Despite the success of these techniques, they appear to be rather disparate, and at present, no general-purpose approach to model reduction for stochastic reaction networks is known. In this paper, we show that most common model reduction approaches for the Chemical Master Equation can be seen as minimizing a well-known information-theoretic quantity between the full model and its reduction, the Kullback–Leibler divergence defined on the space of trajectories. This allows us to recast the task of model reduction as a variational problem that can be tackled using standard numerical optimization approaches. In addition, we derive general expressions for propensities of a reduced system that generalize those found using classical methods. We show that the Kullback–Leibler divergence is a useful metric to assess model discrepancy and to compare different model reduction techniques using three examples from the literature: an autoregulatory feedback loop, the Michaelis–Menten enzyme system, and a genetic oscillator. [ABSTRACT FROM AUTHOR]

This paper concerns the representation of angular momentum operators in the Born–Oppenheimer theory of polyatomic molecules and the various forms of the associated conservation laws. Topics addressed include the question of whether these conservation laws are exactly equivalent or only to some order of the Born–Oppenheimer parameter κ = (m/M)1/4 and what the correlation is between angular momentum quantum numbers in the various representations. These questions are addressed in both problems involving a single potential energy surface and those with multiple, strongly coupled surfaces and in both the electrostatic model and those for which fine structure and electron spin are important. The analysis leads to an examination of the transformation laws under rotations of the electronic Hamiltonian; of the basis states, both adiabatic and diabatic, along with their phase conventions; of the potential energy matrix; and of the derivative couplings. These transformation laws are placed in the geometrical context of the structures in the nuclear configuration space that are induced by rotations, which include the rotational orbits or fibers, the surfaces upon which the orientation of the molecule changes but not its shape, and the section, an initial value surface that cuts transversally through the fibers. Finally, it is suggested that the usual Born–Oppenheimer approximation can be replaced by a dressing transformation, that is, a sequence of unitary transformations that block-diagonalize the Hamiltonian. When the dressing transformation is carried out, we find that the angular momentum operator does not change. This is a part of a system of exact equivalences among various representations of angular momentum operators in Born–Oppenheimer theory. Our analysis accommodates large-amplitude motions and is not dependent on small-amplitude expansions about an equilibrium position. Our analysis applies to noncollinear configurations of a polyatomic molecule; this covers all but a subset of measure zero (the collinear configurations) in the nuclear configuration space. [ABSTRACT FROM AUTHOR]

The interactions between molecules and electrode surfaces play a key role in electrochemical processes and are a subject of extensive research, both experimental and theoretical. In this paper, we address the water dissociation reaction on a Pd(111) electrode surface, modeled as a slab embedded in an external electric field. We aim at unraveling the relationship between surface charge and zero-point energy in aiding or hindering this reaction. We calculate the energy barriers with dispersion-corrected density-functional theory and an efficient parallel implementation of the nudged-elastic-band method. We show that the lowest dissociation barrier and consequently the highest reaction rate take place when the field reaches a strength where two different geometries of the water molecule in the reactant state are equally stable. The zero-point energy contributions to this reaction, on the other hand, remain nearly constant across a wide range of electric field strengths, despite significant changes in the reactant state. Interestingly, we show that the application of electric fields that induce a negative charge on the surface can make nuclear tunneling more significant for these reactions. [ABSTRACT FROM AUTHOR]

Anti-freeze proteins (AFPs) protect organisms at freezing conditions by attaching to the ice surface and arresting its growth. Each adsorbed AFP locally pins the ice surface, resulting in a metastable dimple for which the interfacial forces counteract the driving force for growth. As supercooling increases, these metastable dimples become deeper, until metastability is lost in an engulfment event where the ice irreversibly swallows the AFP. Engulfment resembles nucleation in some respects, and this paper develops a model for the "critical profile" and free energy barrier for the engulfment process. Specifically, we variationally optimize the ice–water interface and estimate the free energy barrier as a function of the supercooling, the AFP footprint size, and the distance to neighboring AFPs on the ice surface. Finally, we use symbolic regression to derive a simple closed-form expression for the free energy barrier as a function of two physically interpretable, dimensionless parameters. [ABSTRACT FROM AUTHOR]

Trapping diffusive particles at surfaces is a key step in many systems in chemical and biological physics. Trapping often occurs via reactive patches on the surface and/or the particle. The theory of boundary homogenization has been used in many prior works to estimate the effective trapping rate for such a system in the case that either (i) the surface is patchy and the particle is uniformly reactive or (ii) the particle is patchy and the surface is uniformly reactive. In this paper, we estimate the trapping rate for the case that the surface and the particle are both patchy. In particular, the particle diffuses translationally and rotationally and reacts with the surface when a patch on the particle contacts a patch on the surface. We first formulate a stochastic model and derive a five-dimensional partial differential equation describing the reaction time. We then use matched asymptotic analysis to derive the effective trapping rate, assuming that the patches are roughly evenly distributed and occupy a small fraction of the surface and the particle. This trapping rate involves the electrostatic capacitance of a four-dimensional duocylinder, which we compute using a kinetic Monte Carlo algorithm. We further use Brownian local time theory to derive a simple heuristic estimate of the trapping rate and show that it is remarkably close to the asymptotic estimate. Finally, we develop a kinetic Monte Carlo algorithm to simulate the full stochastic system and then use these simulations to confirm the accuracy of our trapping rate estimates and homogenization theory. [ABSTRACT FROM AUTHOR]

In this paper, we propose to compute the electronic circular dichroism (ECD) spectra of chiral molecules using a real-time propagation of the time-dependent Schrödinger equation (TDSE) in the space of electronic field-free eigenstates, by coupling TDSE with a given treatment of the electronic structure of the target. The time-dependent induced magnetic moment is used to compute the ECD spectrum from an explicit electric perturbation. The full matrix representing the transition magnetic moment in the space of electronic states is generated from that among pairs of molecular orbitals. In the present work, we show the ECD spectra of methyloxirane, of several conformers of L-alanine, and of the Λ-Co(acac)3 complex, computed from a singly excited ansatz of time-dependent density functional theory eigenstates. The time-domain ECD spectra properly reproduce the frequency-domain ones obtained in the linear-response regime and quantitatively agree with the available experimental data. Moreover, the time-domain approach to ECD allows us to naturally go beyond the ground-state rotationally averaged ECD spectrum, which is the standard outcome of the linear-response theory, e.g., by computing the ECD spectra from electronic excited states. [ABSTRACT FROM AUTHOR]

In this paper, we present a comprehensive account of quantum dissipation theories with the quadratic environment couplings. The theoretical development includes the Brownian solvation mode embedded hierarchical quantum master equations, a core-system hierarchy construction that verifies the extended dissipaton equation of motion (DEOM) formalism [R. X. Xu et al., J. Chem. Phys. 148, 114103 (2018)]. Developed are also the quadratic imaginary-time DEOM for equilibrium and the λ(t)-DEOM for nonequilibrium thermodynamics problems. Both the celebrated Jarzynski equality and Crooks relation are accurately reproduced, which, in turn, confirms the rigorousness of the extended DEOM theories. While the extended DEOM is more numerically efficient, the core-system hierarchy quantum master equation is favorable for "visualizing" the correlated solvation dynamics. [ABSTRACT FROM AUTHOR]

The electrical manipulation of magnetization is appealing to the relevant experiment and spintronic device. In this paper, we focus on the electrical and magnetic properties of a thin film cleaved from the nonmagnetic half-Heusler compound CoTiSb. By means of the first-principles calculations, we find that the surface of TiSb termination possesses ferrimagnetism with a magnetic moment of 0.35 (0.49) μB per unit cell without (with) Hubbard U, which can persist below the Curie temperature of 48 (54) K. What is more, such a surface magnetism can be tuned to nonmagnetism by gate-induced hole doping with a concentration of 2.83 × 1014 (3.55 × 1014) cm−2. This magnetic tunability of the CoTiSb slab provides a platform to realize the pseudo-spin valve with both the magnetic electrodes and nonmagnetic space layer made of the same material without hetero-interfaces. [ABSTRACT FROM AUTHOR]

With an ever-increasing interest in water properties, many intermolecular force fields have been proposed to describe the behavior of water. Unfortunately, good models for liquid water usually cannot provide simultaneously an accurate melting point for ice. For this reason, the TIP4P/Ice model was developed for targeting the melting point and has become the preferred choice for simulating ice at coexistence. Unfortunately, available data for its dynamic properties in the liquid state are scarce. Therefore, we demonstrate a series of simulations aimed at the calculation of transport coefficients for the TIP4P/Ice model over a large range of thermodynamic conditions, ranging from T = 245 K to T = 350 K, for the temperature, and from p = 0 to p = 500 MPa, for the pressure. We have found that the self-diffusion (shear viscosity) exhibits smaller (increased) values than TIP4P/2005 and experiments. However, rescaling the temperature with respect to the triple point temperature, as in a corresponding states plot, we find that TIP4P/Ice compares very well with TIP4P/2005 and experiment. Such observations allow us to infer that despite the different original purposes of these two models examined here, one can benefit from a vast number of reports regarding the behavior of transport coefficients for the TIP4P/2005 model and utilize them following the routine described in this paper. [ABSTRACT FROM AUTHOR]

Superionic (SI) water ices—high-temperature, high-pressure phases of water in which oxygen ions occupy a regular crystal lattice whereas the protons flow in a liquid-like manner—have attracted a growing amount of attention over the past few years, in particular due to their possible role in the magnetic anomalies of the ice giants Neptune and Uranus. In this paper, we consider the calculation of the free energies of such phases, exploring hybrid reference systems consisting of a combination of an Einstein solid for the oxygen ions occupying a crystal lattice and a Uhlenbeck-Ford potential for the protonic fluid that avoids irregularities associated with possible particle overlaps. Applying this approach to a recent neural-network potential-energy landscape for SI water ice, we compute Gibbs free energies as a function of temperature for the SI fcc and liquid phases to determine the melting temperature Tm at 340 GPa. The results are consistent with previous estimates and indicate that the entropy difference between both phases is comparatively small, in particular due to the large amplitude of vibration of the oxygen ions in the fcc phase at the melting temperature. [ABSTRACT FROM AUTHOR]

The excitation energy transfer (EET) process for photosynthetic antenna complexes consisting of subunits, each comprised of multiple chromophores, remains challenging to describe. The multichromophoric Förster resonance energy transfer theory is a popular method to describe the EET process in such systems. This paper presents a new time-domain method for calculating energy transfer based on the combination of multichromophoric Förster resonance energy transfer theory and the Numerical Integration of the Schrödinger Equation method. After validating the method on simple model systems, we apply it to the Light-Harvesting antenna 2 (LH2) complex, a light harvesting antenna found in purple bacteria. We use a simple model combining the overdamped Brownian oscillators to describe the dynamic disorder originating from the environmental fluctuations and the transition charge from the electrostatic potential coupling model to determine the interactions between chromophores. We demonstrate that with this model, both the calculated spectra and the EET rates between the two rings within the LH2 complex agree well with experimental results. We further find that the transfer between the strongly coupled rings of neighboring LH2 complexes can also be well described with our method. We conclude that our new method accurately describes the EET rate for biologically relevant multichromophoric systems, which are similar to the LH2 complex. Computationally, the new method is very tractable, especially for slow processes. We foresee that the method can be applied to efficiently calculate transfer in artificial systems as well and may pave the way for calculating multidimensional spectra of extensive multichromophoric systems in the future. [ABSTRACT FROM AUTHOR]

Utilizing localized orbitals, local correlation theory can reduce the unphysically high system-size scaling of post-Hartree–Fock (post-HF) methods to linear scaling in insulating molecules. The sparsity of the four-index electron repulsion integral (ERI) tensor is central to achieving this reduction. For second-order Møller–Plesset theory (MP2), one of the simplest post-HF methods, only the (ia|jb) ERIs are needed, coupling occupied orbitals i, j and virtuals a, b. In this paper, we compare the numerical sparsity (called the "ragged list") and two other approaches revealing the low-rank sparsity of the ERI. The ragged list requires only one set of (localized) virtual orbitals, and we find that the orthogonal valence virtual-hard virtual set of virtuals originally proposed by Subotnik et al. gives the sparsest ERI tensor. To further compress the ERI tensor, the pair natural orbital (PNO) type representation uses different sets of virtual orbitals for different occupied orbital pairs, while the occupied-specific virtual (OSV) approach uses different virtuals for each occupied orbital. Our results indicate that while the low-rank PNO representation achieves significant rank reduction, it also requires more memory than the ragged list. The OSV approach requires similar memory to that of the ragged list, but it involves greater algorithmic complexity. An approximation (called the "fixed sparsity pattern") for solving the local MP2 equations using the numerically sparse ERI tensor is proposed and tested to be sufficiently accurate and to have highly controllable error. A low-scaling local MP2 algorithm based on the ragged list and the fixed sparsity pattern is therefore promising. [ABSTRACT FROM AUTHOR]

Over the last century, quantum theories have revolutionized our understanding of material properties. One of the most striking quantum phenomena occurring in heterogeneous media is the quantum tunneling effect, where carriers can tunnel through potential barriers even if the barrier height exceeds the carrier energy. Interestingly, the tunneling process can be accompanied by the absorption or emission of light. In most tunneling junctions made of noble metal electrodes, these optical phenomena are governed by plasmonic modes, i.e., light-driven collective oscillations of surface electrons. In the emission process, plasmon excitation via inelastic tunneling electrons can improve the efficiency of photon generation, resulting in bright nanoscale optical sources. On the other hand, the incident light can affect the tunneling behavior of plasmonic junctions as well, leading to phenomena such as optical rectification and induced photocurrent. Thus, plasmonic tunneling junctions provide a rich platform for investigating light–matter interactions, paving the way for various applications, including nanoscale light sources, sensors, and chemical reactors. In this paper, we will introduce recent research progress and promising applications based on plasmonic tunneling junctions. [ABSTRACT FROM AUTHOR]

Introducing nanorods into a polymeric matrix can enhance the physical and mechanical properties of the resulting material. In this paper, we focus on understanding the dispersion and orientation patterns of nanorods in an unentangled polymer melt, particularly as a function of nanorod concentration, using molecular dynamics simulations. The system is comprised of flexible polymer chains and multi-thread nanorods that are equilibrated in the NPT ensemble. All interactions are purely repulsive except for those between polymers and rods. Results with attractive vs repulsive polymer–rod interactions are compared and contrasted. The concentration of rods has a direct impact on the phase behavior of the system. At lower concentrations, rods phase separate into nematic clusters, whereas at higher concentrations more isotropic and less structured rod configurations are observed. A detailed examination of the conformation of the polymer chains near the rod surface shows extension of the chains along the director of the rods (especially within clusters). The dispersion and orientation of the nanorods are a result of the competition between depletion entropic forces responsible for the formation of rod clusters, the enthalpic effects that improve mixing of rods and polymer, and entropic losses of polymers interpenetrating rod clusters. [ABSTRACT FROM AUTHOR]

Many phase change materials (PCMs) are found to crystallize without exhibiting a glass transition endotherm upon reheating. In this paper, we review experimental evidence revealing that these PCMs and likely other hyperquenched molecular and metallic systems can crystallize from the glassy state when reheated at a standard rate. Among these evidences, PCMs annealed below the glass transition temperature Tg exhibit slower crystallization kinetics despite an increase in the number of sub-critical nuclei that should promote the crystallization speed. Flash calorimetry uncovers the glass transition endotherm hidden by crystallization and reveals a distinct change in kinetics when crystallization switches from the glassy to the supercooled liquid state. The resulting Tg value also rationalizes the presence of the pre-Tg relaxation exotherm ubiquitous of hyperquenched systems. Finally, the shift in crystallization temperature during annealing exhibits a non-exponential decay that is characteristic of structural relaxation in the glass. Modeling using a modified Turnbull equation for nucleation rate supports the existence of sub-Tg fast crystallization and emphasizes the benefit of a fragile-to-strong transition for PCM applications due to a reduction in crystallization at low temperature (improved data retention) and increasing its speed at high temperature (faster computing). [ABSTRACT FROM AUTHOR]

Electrochemical impedance spectroscopy (EIS) is a powerful characterization technique for the in-depth investigation of kinetic/transport parameters detection, reaction mechanism understanding, and degradation effects exploration in lithium-ion battery (LIB) systems. However, due to the lack of standardized criterion/paradigm, severe misinterpretations occur frequently during an EIS measurement. In this paper, the significance of instrumental accuracy is described and the character/principle of selection on the simulation model is illuminated/proposed, showing that an adequate precision device and an appropriate fitting model are a prerequisite for a correct EIS analysis. Moreover, the drawbacks of conventional two-electrode EIS experiments for typical coin-type cells are rigorously pointed out by comparison with the ideal three-electrode configuration, where the real impedance information of the cathode would be masked by the sum of both the anode film resistance response and the unavoidable inductive loop signal. The three-electrode case enables efficient accurate observations on individual electrodes, thus facilitating abundant and useful information acquisition. Consequently, devices with a sufficient accuracy, rational simulation models, and advanced three-electrode cells are distinctly illustrated as standardized criterion/paradigm for EIS characterizations, which are essentially important for electrode and interface modifications in LIBs. [ABSTRACT FROM AUTHOR]

Fewest-switches surface hopping (FSSH) has emerged as one of the leading methods for modeling the quantum dynamics of molecular systems. While its original formulation was limited to adiabatic populations, the growing interest in the application of FSSH to coherent phenomena prompts the question of how one should construct a complete density matrix based on FSSH trajectories. A straightforward solution is to define adiabatic coherences based on wavefunction coefficients. In this paper, we demonstrate that inconsistencies introduced in the density matrix through such treatment may lead to a violation of positivity. We furthermore show that a recently proposed coherent generalization of FSSH results in density matrices that satisfy positivity while yielding improved accuracy throughout much (but not all) of parameter space. [ABSTRACT FROM AUTHOR]

The transport of particles through channels is of paramount importance in physics, chemistry, and surface science due to its broad real world applications. Much insight can be gained by observing the transition paths of a particle through a channel and collecting statistics on the lifetimes in the channel or the escape probabilities from the channel. In this paper, we consider the diffusive transport through a narrow conical channel of a Brownian particle subject to intermittent dynamics, namely, stochastic resetting. As such, resetting brings the particle back to a desired location from where it resumes its diffusive phase. To this end, we extend the Fick–Jacobs theory of channel-facilitated diffusive transport to resetting-induced transport. Exact expressions for the conditional mean first passage times, escape probabilities, and the total average lifetime in the channel are obtained, and their behavior as a function of the resetting rate is highlighted. It is shown that resetting can expedite the transport through the channel—rigorous constraints for such conditions are then illustrated. Furthermore, we observe that a carefully chosen resetting rate can render the average lifetime of the particle inside the channel minimal. Interestingly, the optimal rate undergoes continuous and discontinuous transitions as some relevant system parameters are varied. The validity of our one-dimensional analysis and the corresponding theoretical predictions is supported by three-dimensional Brownian dynamics simulations. We thus believe that resetting can be useful to facilitate particle transport across biological membranes—a phenomenon that can spearhead further theoretical and experimental studies. [ABSTRACT FROM AUTHOR]

Using an approach based on the diffusion analog of the Cattaneo–Vernotte differential model, we find the exact analytical solution to the corresponding time-dependent linear hyperbolic initial boundary value problem, describing irreversible diffusion-controlled reactions under Smoluchowski's boundary condition on a spherical sink. By means of this solution, we extend exact analytical calculations for the time-dependent classical Smoluchowski rate coefficient to the case that includes the so-called inertial effects, occurring in the host media with finite relaxation times. We also present a brief survey of Smoluchowski's theory and its various subsequent refinements, including works devoted to the description of the short-time behavior of Brownian particles. In this paper, we managed to show that a known Rice's formula, commonly recognized earlier as an exact reaction rate coefficient for the case of hyperbolic diffusion, turned out to be only its approximation being a uniform upper bound of the exact value. Here, the obtained formula seems to be of great significance for bridging a known gap between an analytically estimated rate coefficient on the one hand and molecular dynamics simulations together with experimentally observed results for the short times regime on the other hand. A particular emphasis has been placed on the rigorous mathematical treatment and important properties of the relevant initial boundary value problems in parabolic and hyperbolic diffusion theories. [ABSTRACT FROM AUTHOR]

The first paper of this series [J. Chem. Phys. 158, 034103 (2023)] demonstrated that excess entropy scaling holds for both fine-grained and corresponding coarse-grained (CG) systems. Despite its universality, a more exact determination of the scaling relationship was not possible due to the semi-empirical nature. In this second paper, an analytical excess entropy scaling relation is derived for bottom-up CG systems. At the single-site CG resolution, effective hard sphere systems are constructed that yield near-identical dynamical properties as the target CG systems by taking advantage of how hard sphere dynamics and excess entropy can be analytically expressed in terms of the liquid packing fraction. Inspired by classical equilibrium perturbation theories and recent advances in constructing hard sphere models for predicting activated dynamics of supercooled liquids, we propose a new approach for understanding the diffusion of molecular liquids in the normal regime using hard sphere reference fluids. The proposed "fluctuation matching" is designed to have the same amplitude of long wavelength density fluctuations (dimensionless compressibility) as the CG system. Utilizing the Enskog theory to derive an expression for hard sphere diffusion coefficients, a bridge between the CG dynamics and excess entropy is then established. The CG diffusion coefficient can be roughly estimated using various equations of the state, and an accurate prediction of accelerated CG dynamics at different temperatures is also possible in advance of running any CG simulation. By introducing another layer of coarsening, these findings provide a more rigorous method to assess excess entropy scaling and understand the accelerated CG dynamics of molecular fluids. [ABSTRACT FROM AUTHOR]

Coarse-grained (CG) models facilitate an efficient exploration of complex systems by reducing the unnecessary degrees of freedom of the fine-grained (FG) system while recapitulating major structural correlations. Unlike structural properties, assessing dynamic properties in CG modeling is often unfeasible due to the accelerated dynamics of the CG models, which allows for more efficient structural sampling. Therefore, the ultimate goal of the present series of articles is to establish a better correspondence between the FG and CG dynamics. To assess and compare dynamical properties in the FG and the corresponding CG models, we utilize the excess entropy scaling relationship. For Paper I of this series, we provide evidence that the FG and the corresponding CG counterpart follow the same universal scaling relationship. By carefully reviewing and examining the literature, we develop a new theory to calculate excess entropies for the FG and CG systems while accounting for entropy representability. We demonstrate that the excess entropy scaling idea can be readily applied to liquid water and methanol systems at both the FG and CG resolutions. For both liquids, we reveal that the scaling exponents remain unchanged from the coarse-graining process, indicating that the scaling behavior is universal for the same underlying molecular systems. Combining this finding with the concept of mapping entropy in CG models, we show that the missing entropy plays an important role in accelerating the CG dynamics. [ABSTRACT FROM AUTHOR]

In this paper, we investigate prenucleation and heterogeneous nucleation in the liquid Pb/solid Al system as an example of systems with large lattice misfit using molecular dynamics simulation. Solid Pb and Al have a large positive lattice misfit (f) of 18.2% along the densely packed [110] direction. This study reveals that prenucleation occurs at 600 K (an undercooling of 15 K), and a 2-dimensional (2D) ordered structure forms at the interface with a coincidence site lattice (CSL) between the first Pb and first Al layers. The CSL accommodates the major part of the f, and only a small residual lattice misfit (fr) of 1.9% remains. The formation of the CSL transforms the original substrate into a considerably potent nucleant, where the first Pb layer becomes the new surface layer of the substrate. At an undercooling of about 22 K, nucleation proceeds by merging 2D ordered structure through structural templating: the second Pb layer is epitaxial to the CSL Pb layer, the third Pb layer largely accommodates the fr, and the fourth Pb layer is a nearly perfect crystalline plane. Further analysis indicates that the interface with the CSL has a lower interfacial energy than with a cube-to-cube orientation relationship. For the first time, we established that the CSL was an effective mechanism to accommodate the f for systems with a large positive misfits. Heterogeneous nucleation is governed not by a single mechanism (misfit dislocations in Turnbull's model), but instead by various mechanisms depending on f. This study sheds new light on the atomistic mechanism of heterogeneous nucleation. [ABSTRACT FROM AUTHOR]

For many laser-based methods of material characterization and analysis, a tensor formulation of theory is necessary, especially in techniques that exploit nonlinear or chiral optics. The fundamental interactions that underpin such methods offer various levels of approach to theory, but the most rigorous often lead to equations of considerable complexity. To compute the values for individual material parameters frequently demands making assumptions of extreme simplicity, overly dependent on calculational method, yet still providing unsatisfactory results. A pragmatic and entirely rigorous symmetry-based approach to the irreducible tensorial structures circumvents many of these problems, securing reliable results and guiding the pathway to applications. Instead of focusing on individual tensor components, such an approach can rapidly determine the number of linearly independent quantities—and hence the number of operationally different setups necessary for full characterization. By such means, one can directly ascertain how variations of optical polarization and beam geometry can reliably capture the response of any material system. The use of an irreducible tensor method operates independently of any means that might be chosen to calculate material properties. It removes the need for common simplifying assumptions, such as the approximation of tensorial structure by a scalar representation, adoption of a two-state model, or disregarding near-resonance damping. It also obviates any dependence on a choice of simulation package or quantum-calculational software. In this paper, the principles are set down and illustrated by application to experiments of varying degrees of complexity, including interactions of growing significance in the realm of chiral nonlinear optics. Limitations of this approach are also critically assessed. [ABSTRACT FROM AUTHOR]

Efficient energy transport in photosynthetic antenna is a long-standing source of inspiration for artificial light harvesting materials. However, characterizing the excited states of the constituent chromophores poses a considerable challenge to mainstream quantum chemical and semiempirical excited state methods due to their size and complexity and the accuracy required to describe small but functionally important changes in their properties. In this paper, we explore an alternative approach to calculating the excited states of large biochromophores, exemplified by a specific method for calculating the Qy transition of bacteriochlorophyll a, which we name Chl-xTB. Using a diagonally dominant approximation to the Casida equation and a bespoke parameterization scheme, Chl-xTB can match time-dependent density functional theory's accuracy and semiempirical speed for calculating the potential energy surfaces and absorption spectra of chlorophylls. We demonstrate that Chl-xTB (and other prospective realizations of our protocol) can be integrated into multiscale models, including concurrent excitonic and point-charge embedding frameworks, enabling the analysis of biochromophore networks in a native environment. We exploit this capability to probe the low-frequency spectral densities of excitonic energies and interchromophore interactions in the light harvesting antenna protein LH2 (light harvesting complex 2). The impact of low-frequency protein motion on interchromophore coupling and exciton transport has routinely been ignored due to the prohibitive costs of including it in simulations. Our results provide a more rigorous basis for continued use of this approximation by demonstrating that exciton transition energies are unaffected by low-frequency vibrational coupling to exciton interaction energies. [ABSTRACT FROM AUTHOR]

Simulating the unitary dynamics of a quantum system is a fundamental problem of quantum mechanics, in which quantum computers are believed to have significant advantage over their classical counterparts. One prominent such instance is the simulation of electronic dynamics, which plays an essential role in chemical reactions, non-equilibrium dynamics, and material design. These systems are time-dependent, which requires that the corresponding simulation algorithm can be successfully concatenated with itself over different time intervals to reproduce the overall coherent quantum dynamics of the system. In this paper, we quantify such simulation algorithms by the property of being fully-coherent: the algorithm succeeds with arbitrarily high success probability 1 − δ while only requiring a single copy of the initial state. We subsequently develop fully-coherent simulation algorithms based on quantum signal processing (QSP), including a novel algorithm that circumvents the use of amplitude amplification while also achieving a query complexity additive in time t, ln(1/δ), and ln(1/ϵ) for error tolerance ϵ: Θ ‖ H ‖ | t | + ln (1 / ϵ) + ln (1 / δ) . Furthermore, we numerically analyze these algorithms by applying them to the simulation of the spin dynamics of the Heisenberg model and the correlated electronic dynamics of an H2 molecule. Since any electronic Hamiltonian can be mapped to a spin Hamiltonian, our algorithm can efficiently simulate time-dependent ab initio electronic dynamics in the circuit model of quantum computation. Accordingly, it is also our hope that the present work serves as a bridge between QSP-based quantum algorithms and chemical dynamics, stimulating a cross-fertilization between these exciting fields. [ABSTRACT FROM AUTHOR]

Lyotropic liquid crystal phases (LCPs) are widely studied for diverse applications, including protein crystallization and drug delivery. The structure and properties of LCPs vary widely depending on the composition, concentration, temperature, pH, and pressure. High-throughput structural characterization approaches, such as small-angle x-ray scattering (SAXS), are important to cover meaningfully large compositional spaces. However, high-throughput LCP phase analysis for SAXS data is currently lacking, particularly for patterns of multiphase mixtures. In this paper, we develop semi-automated software for high throughput LCP phase identification from SAXS data. We validate the accuracy and time-savings of this software on a total of 668 SAXS patterns for the LCPs of the amphiphile hexadecyltrimethylammonium bromide (CTAB) in 53 acidic or basic ionic liquid derived solvents, within a temperature range of 25–75 °C. The solvents were derived from stoichiometric ethylammonium nitrate (EAN) or ethanolammonium nitrate (EtAN) by adding water to vary the ionicity, and adding precursor ions of ethylamine, ethanolamine, and nitric acid to vary the pH. The thermal stability ranges and lattice parameters for CTAB-based LCPs obtained from the semi-automated analysis showed equivalent accuracy to manual analysis, the results of which were previously published. A time comparison of 40 CTAB systems demonstrated that the automated phase identification procedure was more than 20 times faster than manual analysis. Moreover, the high throughput identification procedure was also applied to 300 unpublished scattering patterns of sodium dodecyl-sulfate in the same EAN and EtAN based solvents in this study, to construct phase diagrams that exhibit phase transitions from micellar, to hexagonal, cubic, and lamellar LCPs. The accuracy and significantly low analysis time of the high throughput identification procedure validates a new, rapid, unrestricted analytical method for the determination of LCPs. [ABSTRACT FROM AUTHOR]

This paper presents a theoretical investigation of the design of a new actuator type made of anisotropic colloidal particles grafted with stimuli-responsive polymer chains. These artificial muscles combine the osmotic actuation principle of stimuli-responsive hydrogels with the structural alignment of colloidal liquid crystals to achieve directional motion. The solubility of the stimuli-responsive polymer in the neutral state, its degree of polymerization, the salt concentration, and the grafting density of the polymer chains on the surface of the colloidal particles are investigated and identified as important for actuator performance and tunability. The computational results suggest that the proposed mechanically active material matches or exceeds the performances of natural muscles and provide the guidelines for the realization of artificial muscles with predetermined actuation properties. [ABSTRACT FROM AUTHOR]

Light-induced orientation of gas phase molecules is a long-pursued goal in physics and chemistry. Here, we experimentally demonstrate a six-fold increase in the terahertz-induced orientation of iodomethane (CH3I) molecules at room temperature, provided by rotational pre-excitation with a moderately intense near-IR pulse. The paper highlights the underlying interference of multiple coherent transition pathways within the rotational coherence manifold and is analyzed accordingly. Our experimental and theoretical results provide desirable and practical means for all-optical experiments on oriented molecular ensembles. [ABSTRACT FROM AUTHOR]

This paper presents a state-averaged complete active space self-consistent field (SA-CASSCF) in the atomic multipole optimized energetics for biomolecular application (AMOEBA) polarizable water model, which enables rigorous simulation of non-adiabatic molecular dynamics with nonequilibrium solvation effects. The molecular orbital and configuration interaction coefficients of the solute wavefunction, and the induced dipoles on solvent atoms, are solved by minimizing the state averaged energy variationally. In particular, by formulating AMOEBA water models and the polarizable continuum model (PCM) in a unified way, the algorithms developed for computing SA-CASSCF/PCM energies, analytical gradients, and non-adiabatic couplings in our previous work can be generalized to SA-CASSCF/AMOEBA by properly substituting a specific list of variables. Implementation of this method will be discussed with the emphasis on how the calculations of different terms are partitioned between the quantum chemistry and molecular mechanics codes. We will present and discuss results that demonstrate the accuracy and performance of the implementation. Next, we will discuss results that compare three solvent models that work with SA-CASSCF, i.e., PCM, fixed-charge force fields, and the newly implemented AMOEBA. Finally, the new SA-CASSCF/AMOEBA method has been interfaced with the ab initio multiple spawning method to carry out non-adiabatic molecular dynamics simulations. This method is demonstrated by simulating the photodynamics of the model retinal protonated Schiff base molecule in water. [ABSTRACT FROM AUTHOR]

In this (Paper II) and the preceding companion paper (Paper I; R. May, R. Smith, and B. Kay, J. Chem. Phys. 138, 104501 (2013)), we investigate the mechanisms for the release of trapped gases from underneath amorphous solid water (ASW) films. In Paper I, we focused on the low coverage regime where the release mechanism is controlled by crystallization-induced cracks formed in the ASW overlayer. In that regime, the results were largely independent of the particular gas underlayer. Here in Paper II, we focus on the high coverage regime where new desorption pathways become accessible prior to ASW crystallization. In contrast to the results for the low coverage regime (Paper I), the release mechanism is a function of the multilayer thickness and composition, displaying dramatically different behavior between Ar, Kr, Xe, CH4, N2, O2, and CO. Two primary desorption pathways are observed. The first occurs between 100 and 150 K and manifests itself as sharp, extremely narrow desorption peaks. Temperature programmed desorption is utilized to show that these abrupt desorption bursts are due to pressure induced structural failure of the ASW overlayer. The second pathway occurs at low temperature (typically <100 K) where broad desorption peaks are observed. Desorption through this pathway is attributed to diffusion through pores formed during ASW deposition. The extent of desorption and the line shape of the low temperature desorption peak are dependent on the substrate on which the gas underlayer is deposited. Angle dependent ballistic deposition of ASW is used to vary the porosity of the overlayer and strongly supports the hypothesis that the low temperature desorption pathway is due to porosity that is templated into the ASW overlayer by the underlayer during deposition. [ABSTRACT FROM AUTHOR]

Allowing triplet components of individual geminals, spin-contaminated strongly orthogonal geminal wave functions may emerge, which can be ameliorated by spin-projection techniques. Of the latter, half-projection was previously shown to be useful, offering a compromise between the amount of remaining spin-contamination and the violation of size consistency generated by projection. This paper investigates how a half-projected spin-contaminated geminal wave function can be improved by multi-configuration perturbation theory to incorporate dynamical correlation effects. [ABSTRACT FROM AUTHOR]

The generalized quantum master equation (GQME) provides a general and formally exact framework for simulating the reduced dynamics of open quantum systems. The recently introduced modified approach to the GQME (M-GQME) corresponds to a specific implementation of the GQME that is geared toward simulating the dynamics of the electronic reduced density matrix in systems governed by an excitonic Hamiltonian. Such a Hamiltonian, which is often used for describing energy and charge transfer dynamics in complex molecular systems, is given in terms of diabatic electronic states that are coupled to each other and correspond to different nuclear Hamiltonians. Within the M-GQME approach, the effect of the nuclear degrees of freedom on the time evolution of the electronic density matrix is fully captured by a memory kernel superoperator, which can be obtained from short-lived (compared to the time scale of energy/charge transfer) projection-free inputs. In this paper, we test the ability of the M-GQME to predict the energy transfer dynamics within a seven-state benchmark model of the Fenna–Matthews–Olson (FMO) complex, with the short-lived projection-free inputs obtained via the Ehrenfest method. The M-GQME with Ehrenfest-based inputs is shown to yield accurate results across a wide parameter range. It is also found to dramatically outperform the direct application of the Ehrenfest method and to provide better-behaved convergence with respect to memory time in comparison to an alternative implementation of the GQME approach previously applied to the same FMO model. [ABSTRACT FROM AUTHOR]

The Infrared (IR) and Raman spectra of various defects in silicon, containing both oxygen atoms (in the interstitial position, Oi) and a vacancy, are computed at the quantum mechanical level by using a periodic supercell approach based on a hybrid functional (B3LYP), an all-electron Gaussian-type basis set, and the Crystal code. The first of these defects is VO: the oxygen atom, twofold coordinated, saturates the unpaired electrons of two of the four carbon atoms on first neighbors of the vacancy. The two remaining unpaired electrons on the first neighbors of the vacancy can combine to give a triplet (Sz = 1) or a singlet (Sz = 0) state; both states are investigated for the neutral form of the defect, together with the doublet solution, the ground state of the negatively charged defect. Defects containing two, three, and four oxygen atoms, in conjunction with the vacancy V, are also investigated as reported in many experimental papers: VO2 and VOOi (two oxygen atoms inside the vacancy, or one in the vacancy and one in interstitial position between two Si atoms) and VO2Oi and VO22Oi (containing three and four oxygen atoms). This study integrates and complements a recent investigation referring to Oi defects [Gentile et al., J. Chem. Phys. 152, 054502 (2020)]. A general good agreement is observed between the simulated IR spectra and experimental observations referring to VOx (x = 1–4) defects. [ABSTRACT FROM AUTHOR]

This is the final paper in a series that introduces geodesic molecular dynamics at constant potential energy. This dynamics is entitled NVU dynamics in analogy to standard energy-conserving Newtonian NVE dynamics. In the first two papers [T. S. Ingebrigtsen, S. Toxvaerd, O. J. Heilmann, T. B. Schro\der, and J. C. Dyre, J. Chem. Phys. 135, 104101 (2011); T. S. Ingebrigtsen, S. Toxvaerd, T. B. Schro\der, and J. C. Dyre, ibid. 135, 104102 (2011)], a numerical algorithm for simulating geodesic motion of atomic systems was developed and tested against standard algorithms. The conclusion was that the NVU algorithm has the same desirable properties as the Verlet algorithm for Newtonian NVE dynamics, i.e., it is time-reversible and symplectic. Additionally, it was concluded that NVU dynamics becomes equivalent to NVE dynamics in the thermodynamic limit. In this paper, the NVU algorithm for atomic systems is extended to be able to simulate the geodesic motion of molecules at constant potential energy. We derive an algorithm for simulating rigid bonds and test this algorithm on three different systems: an asymmetric dumbbell model, Lewis-Wahnström o-terphenyl (OTP) and rigid SPC/E water. The rigid bonds introduce additional constraints beyond that of constant potential energy for atomic systems. The rigid-bond NVU algorithm conserves potential energy, bond lengths, and step length for indefinitely long runs. The quantities probed in simulations give results identical to those of Nosé-Hoover NVT dynamics. Since Nosé-Hoover NVT dynamics is known to give results equivalent to those of NVE dynamics, the latter results show that NVU dynamics becomes equivalent to NVE dynamics in the thermodynamic limit also for molecular systems. [ABSTRACT FROM AUTHOR]

Photodetachment bands of anionic boron clusters, Bn (n = 4,5) are theoretically examined here. The model Hamiltonians developed through extensive ab initio quantum chemistry calculations in Paper I are employed for the required nuclear dynamics study. While the precise location of vibronic lines and progression of vibrational modes within a given electronic band is derived from time-independent quantum mechanical studies, the broadband spectral envelopes and the nonradiative decay rate of electronic states are calculated by propagating wave packets in a time-dependent quantum mechanical framework. The theoretical results are in good accord with the experiment to a large extent. The discrepancies between the two can be partly attributed to the inadequate energy resolution of the experimental results and also to the neglect of dynamic spin-orbit interactions and computational difficulty related with detachment channels involving multi-electron transitions in the theoretical formalism. [ABSTRACT FROM AUTHOR]

This series of papers is devoted to identifying and explaining the properties of strongly correlating liquids, i.e., liquids with more than 90% correlation between their virial W and potential energy U fluctuations in the NVT ensemble. Paper IV [N. Gnan et al., J. Chem. Phys. 131, 234504 (2009)] showed that strongly correlating liquids have 'isomorphs,' which are curves in the phase diagram along which structure, dynamics, and some thermodynamic properties are invariant in reduced units. In the present paper, using the fact that reduced-unit radial distribution functions are isomorph invariant, we derive an expression for the shapes of isomorphs in the WU phase diagram of generalized Lennard-Jones systems of one or more types of particles. The isomorph shape depends only on the Lennard-Jones exponents; thus all isomorphs of standard Lennard-Jones systems (with exponents 12 and 6) can be scaled onto a single curve. Two applications are given. One tests the prediction that the solid-liquid coexistence curve follows an isomorph by comparing to recent simulations by Ahmed and Sadus [J. Chem. Phys. 131, 174504 (2009)]. Excellent agreement is found on the liquid side of the coexistence curve, whereas the agreement is less convincing on the solid side. A second application is the derivation of an approximate equation of state for generalized Lennard-Jones systems by combining the isomorph theory with the Rosenfeld-Tarazona expression for the temperature dependence of the potential energy on isochores. It is shown that the new equation of state agrees well with simulations. [ABSTRACT FROM AUTHOR]

Nuclear dynamics in the coupled electronic states of mono-, di-(ortho and meta), and pentafluorobenzene molecules is investigated here. Attempts are specifically made to understand the complexity and broadening of the recorded gas phase electronic absorption spectra of these molecules. Justification is also provided for the low quantum yield of fluorescence emission with increasing number of fluorine substitutions. The nuclear dynamics is simulated from first principles both by time-independent and time-dependent quantum mechanical methods. Potential energy surfaces of the low-lying excited electronic states of these molecules constructed in Paper I [Mondal and Mahapatra, J. Chem. Phys. 133, 084304 (2010)] are employed for the purpose. Theoretical results presented in this paper are compared with the available experimental data and the agreement between the two is found to be excellent. While structured electronic absorption bands are observed for the S1 state of mono- and difluorobenzene molecules, the same for the pentafluorobenzene is broad and structureless. Occurrence of S1-S2 conical intersections in pentafluorobenzene leads to a nonradiative internal conversion of the S1 state in ∼165 fs and contributes to the broadening of the S1←S0 absorption band and a biexponential decay of its fluorescence emission. [ABSTRACT FROM AUTHOR]

This paper presents a theoretical description of diffusion growth of a gas bubble after its nucleation in supersaturated liquid solution. We study systems where gas molecules completely dissociate in the solvent into two parts, thus making Sievert’s solubility law valid. We show that the difference between Henry’s and Sievert’s laws for chemical equilibrium conditions causes the difference in bubble growth dynamics. Assuming that diffusion flux is steady we obtain a differential equation on bubble radius. Bubble dynamics equation is solved analytically for the case of homogeneous nucleation of a bubble, which takes place at a significant pressure drop. We also obtain conditions of diffusion flux steadiness. The fulfillment of these conditions is studied for the case of nucleation of water vapor bubbles in magmatic melts. [ABSTRACT FROM AUTHOR]