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In quantum chemistry, Lowest Unoccupied Molecular Orbital (LUMO) is important for studying various chemical processes, including photochemical reactions, electron attached states, and electron excites states. Recently, an effective method has been introduced that involves the use of the Parametric Equation of Motion (PEM) in conjunction with the nuclear charge stabilization method for precise identification of true LUMO. However, the inclusion of extra diffuse functions in the basis set, which is necessary for describing electron-attached and electron-excited states, can cause issues due to the presence of the same symmetry states, leading to avoided crossing. Identifying the true LUMO among these avoided crossings is challenging due to the mixing of states and the exchange of their orbital character. This article introduces a modification of the PEM to identify the true LUMO by preventing the stabilization of specific states involved in avoided crossings. The present method is highly effective and requires minimal computational cost. [ABSTRACT FROM AUTHOR]

Evaluation of the charge transport property of organic semiconductors requires exact quantum dynamics simulation of large systems. We present a numerically nearly exact approach to investigate carrier transport dynamics in organic semiconductors by extending the non-Markovian stochastic Schrödinger equation with complex frequency modes to a forward–backward scheme and by solving it using the matrix product state (MPS) approach. By utilizing the forward–backward formalism for noise generation, the bath correlation function can be effectively treated as a temperature-independent imaginary part, enabling a more accurate decomposition with fewer complex frequency modes. Using this approach, we study the carrier transport and mobility in the one-dimensional Peierls model, where the nonlocal electron–phonon interaction is taken into account. The reliability of this approach was validated by comparing carrier diffusion motion with those obtained from the hierarchical equations of motion method across various parameter regimes of the phonon bath. The efficiency was demonstrated by the modest virtual bond dimensions of MPS and the low scaling of the computational time with the system size. [ABSTRACT FROM AUTHOR]

We here present the normal dynamics technique, which recasts the Newton's equations of motion in terms of phonon normal modes by exploiting a proper sampling of the reciprocal space. After introducing the theoretical background, we discuss how the reciprocal space sampling enables us to (i) obtain a computational speedup by selecting which and how many wave vectors of the Brillouin zone will be considered and (ii) account for distortions realized across large atomic distances without the use of large simulation cells. We implemented the approach into an open-source code, which we used to present three case studies: in the first one, we elucidate the general strategy for the sampling of the reciprocal space; in the second one, we illustrate the potential of the approach by studying the stabilization effect of temperature in α-uranium; and in the last one, we investigate the characterization of Raman spectra at different temperatures in MoS2/MX2 transition metal dichalcogenide heterostructures. Finally, we discuss how the procedure is general and can be used to simulate periodic, semiperiodic, and finite systems such as crystals, slabs, nanoclusters, or molecules. [ABSTRACT FROM AUTHOR]

We theoretically study the conformational and dynamical properties of semiflexible active polar ring polymers under linear shear flow. A ring is described as a continuous semiflexible Gaussian polymer with a tangential active force of a constant density along its contour. The linear but non-Hermitian equation of motion is solved using an eigenfunction expansion, which yields activity-independent, but shear-rate-dependent, relaxation times and activity-dependent frequencies. As a consequence, the ring's stationary-state properties are independent of activity, and its conformations and rheological properties are equal to those of a passive ring under shear. The presence of characteristic time scales by relaxation and the activity-dependent frequencies give rise to a particular dynamical behavior. A tank-treading-like motion emerges for long relaxation times and high activities, specifically for stiff rings. In the case of very flexible polymers, the relaxation behavior dominates over activity contributions suppressing tank-treading. Shear strongly affects the crossover from a tank-treading to a relaxation-dominated dynamics, and the ring polymer exhibits tumbling motion at high shear rates. This is reflected in the tumbling frequency, which displays two shear-rate dependent regimes, with an activity-dependent plateau at low shear rates followed by a power-law regime with increasing tumbling frequency for high shear rates. [ABSTRACT FROM AUTHOR]

The motional narrowing effect has been extensively studied for cavity exciton–polariton systems in recent decades both experimentally and theoretically, which is featured by (1) the subaverage behavior and (2) the asymmetric linewidths for the upper polariton and the lower polariton. However, a minimal theoretical model that is clear and adequate to address all these effects as well as the linewidth scaling relations remains missing. In this work, based on the single mode 1D Holstein–Tavis–Cummings (HTC) model, we studied the motional narrowing effect of the polariton linear absorption spectra via both semi-analytic derivations and numerically exact quantum dynamics simulations using the hierarchical equations of motion approach. The results reveal that under collective light–matter coupling between a cavity mode and N molecules, the polariton linewidth scales as 1 / N under the slow limit, while scales as 1/N under the fast limit, due to the polaron decoupling effect. Furthermore, by varying the detunings, the polariton linewidths exhibit significant motional narrowing, covering both characters mentioned above. Our analytic linewidth expressions [Eqs. (34) and (35)] agree well with the numerical exact simulations in all the parameter regimes we explored. These results indicate that the physics of motional narrowing is adequately accounted for by the single-mode 1D HTC model. We envision that both the numerical results and the analytic polariton linewidths expression presented in this work will offer great theoretical value for providing a better understanding of the exciton–polariton motional narrowing based on the HTC model. [ABSTRACT FROM AUTHOR]

Strong coupling between the molecular system and photon inside the cavity generates polaritons, which can alter reaction rates by orders of magnitude. In this work, we benchmark the surface hopping method to simulate non-adiabatic dynamics in a cavity. The comparison is made against a numerically exact method (the hierarchical equations of motion) for a model system investigating excitonic energy transfer for a broad range of parameters. Surface hopping captures the effects of the radiation mode well, both at resonance and off-resonance. We have further investigated parameters that can increase or decrease the rate of population transfer, and we find that surface hopping in general can capture both effects well. Finally, we show that the dipole self-energy term within our parameter regime does not significantly affect the system's dynamics. [ABSTRACT FROM AUTHOR]

Conical intersections (CIs) play a crucial role in photochemical reactions, offering an efficient channel for ultrafast non-adiabatic relaxation of excited states. This significantly influences the reaction pathways and the resulting products. In this work, we utilize the non-Markovian stochastic Schrödinger equation with complex modes method to explore the dynamics of electronic transitions through conical intersections (CIs) in pyrazine. The linear vibronic coupling model serves as the foundational framework, incorporating both intra-state and inter-state electron–vibrational interactions. The dynamics of the excited electronic transitions are analyzed across varying strengths of system–bath coupling and different bath relaxation times. The accuracy of this method is demonstrated by comparing its predictions with those from the hierarchical equations of motion method. [ABSTRACT FROM AUTHOR]

In this work, we present a mixed quantum–classical open quantum system dynamics method for studying rate modifications of ground-state chemical reactions in an optical cavity under vibrational strong-coupling conditions. In this approach, the cavity radiation mode is treated classically with a mean-field nuclear force averaging over the remaining degrees of freedom, both within the system and the environment, which are handled quantum mechanically within the hierarchical equations of motion framework. Using this approach, we conduct a comparative analysis by juxtaposing the mixed quantum–classical results with fully quantum-mechanical simulations. After eliminating spurious peaks that can occur when not using the rigorous definition of the rate constant, we confirm the crucial role of the quantum nature of the cavity radiation mode in reproducing the resonant peak observed in the cavity frequency-dependent rate profile. In other words, it appears necessary to explicitly consider the quantized photonic states in studying reactivity modification in vibrational polariton chemistry (at least for the model systems studied in this work), as these phenomena stem from cavity-induced reaction pathways involving resonant energy exchanges between photons and molecular vibrational transitions. [ABSTRACT FROM AUTHOR]

Voltage distribution in sub-cellular micro-domains such as neuronal synapses, small protrusions, or dendritic spines regulates the opening and closing of ionic channels, energy production, and thus, cellular homeostasis and excitability. Yet how voltage changes at such a small scale in vivo remains challenging due to the experimental diffraction limit, large signal fluctuations, and the still limited resolution of fast voltage indicators. Here, we study the voltage distribution in nano-compartments using a computational approach based on the Poisson–Nernst–Planck equations for the electro-diffusion motion of ions, where inward and outward fluxes are generated between channels. We report a current–voltage (I–V) logarithmic relationship generalizing Nernst law that reveals how the local membrane curvature modulates the voltage. We further find that an influx current penetrating a cellular electrolyte can lead to perturbations from tens to hundreds of nanometers deep, depending on the local channel organization. Finally, we show that the neck resistance of dendritic spines can be completely shunted by the transporters located on the head boundary, facilitating ionic flow. To conclude, we propose that voltage is regulated at a subcellular level by channel organization, membrane curvature, and narrow passages. [ABSTRACT FROM AUTHOR]

The projected complex absorbing potential (CAP) technique is one of the methods that allow one to extend the bound state methods for computing resonances' energies and widths. Here, we explore the accuracy of the potential energy curves generated with different electronic structure theory methods in combination with the projected CAP technique by considering resonant vibrational excitation (RVE) of N2 by electron impact as a model process. We report RVE cross sections computed using the boomerang model with potential energy curves obtained with CAP-based extended multistate complete active space perturbation theory (XMS-CASPT2) and equation of motion coupled-cluster method for electron attachment with single and double substitution (EOM-EA-CCSD) methods. We also compare potential energy curves computed with several electronic structure methods, including XMS-CASPT2, EOM-EA-CCSD, multireference configuration interaction with singles (MR-CIS) and singles and doubles (MR-CISD). A good agreement is observed between the experiment and simulated RVE cross sections obtained with the potential energy curves generated with XMS-CASPT2 and EOM-EA-CCSD methods, thus highlighting the potential of the projected CAP technique combined with accurate electronic structure methods for dynamical simulations of the processes that proceed through metastable electronic states. [ABSTRACT FROM AUTHOR]

The projected complex absorbing potential (CAP) technique is one of the methods that allow one to extend the bound state methods for computing resonances' energies and widths. Here, we explore the accuracy of the potential energy curves generated with different electronic structure theory methods in combination with the projected CAP technique by considering resonant vibrational excitation (RVE) of N2 by electron impact as a model process. We report RVE cross sections computed using the boomerang model with potential energy curves obtained with CAP-based extended multistate complete active space perturbation theory (XMS-CASPT2) and equation of motion coupled-cluster method for electron attachment with single and double substitution (EOM-EA-CCSD) methods. We also compare potential energy curves computed with several electronic structure methods, including XMS-CASPT2, EOM-EA-CCSD, multireference configuration interaction with singles (MR-CIS) and singles and doubles (MR-CISD). A good agreement is observed between the experiment and simulated RVE cross sections obtained with the potential energy curves generated with XMS-CASPT2 and EOM-EA-CCSD methods, thus highlighting the potential of the projected CAP technique combined with accurate electronic structure methods for dynamical simulations of the processes that proceed through metastable electronic states. [ABSTRACT FROM AUTHOR]

In non-perturbative non-Markovian open quantum systems, reaching either low temperatures with the hierarchical equations of motion (HEOM) or high temperatures with the Thermalized Time Evolving Density Operator with Orthogonal Polynomials Algorithm (T-TEDOPA) formalism in Hilbert space remains challenging. We compare different ways of modeling the environment. Sampling the Fourier transform of the bath correlation function, also called temperature dependent spectral density, proves to be very effective. T-TEDOPA [Tamascelli et al., Phys. Rev. Lett. 123, 090402 (2019)] uses a linear chain of oscillators with positive and negative frequencies, while HEOM is based on the complex poles of an optimized rational decomposition of the temperature dependent spectral density [Xu et al., Phys. Rev. Lett. 129, 230601 (2022)]. Resorting to the poles of the temperature independent spectral density and of the Bose function separately is an alternative when the problem due to the huge number of Bose poles at low temperatures is circumvented. Two examples illustrate the effectiveness of the HEOM and T-TEDOPA approaches: a benchmark pure dephasing case and a two-bath model simulating the dynamics of excited electronic states coupled through a conical intersection. We show the efficiency of T-TEDOPA to simulate dynamics at a finite temperature by using either continuous spectral densities or only all the intramolecular oscillators of a linear vibronic model calibrated from ab initio data of a phenylene ethynylene dimer. [ABSTRACT FROM AUTHOR]

In the previous paper [C. W. Kim and I. Franco, J. Chem. Phys. 160, 214111-1–214111-13 (2024)], we developed a theory called MQME-D, which allows us to decompose the overall energy dissipation process in open quantum system dynamics into contributions by individual components of the bath when the subsystem dynamics is governed by a Markovian quantum master equation (MQME). Here, we contrast the predictions of MQME-D against the numerically exact results obtained by combining hierarchical equations of motion (HEOM) with a recently reported protocol for monitoring the statistics of the bath. Overall, MQME-D accurately captures the contributions of specific bath components to the overall dissipation while greatly reducing the computational cost compared to exact computations using HEOM. The computations show that MQME-D exhibits errors originating from its inherent Markov approximation. We demonstrate that its accuracy can be significantly increased by incorporating non-Markovianity by exploiting time scale separations (TSS) in different components of the bath. Our work demonstrates that MQME-D combined with TSS can be reliably used to understand how energy is dissipated in realistic open quantum system dynamics. [ABSTRACT FROM AUTHOR]

Static and time-dependent quantum-mechanical approaches have been employed in the literature to characterize the physics of light-emitting molecules and nanostructures. However, the electromagnetic emission induced by an input current has remained beyond the realm of molecular simulations. This is the challenge addressed here with the help of an equation of motion for the density matrix coupled to a photon bath based on a Redfield formulation. This equation is evolved within the framework of the driven-Liouville von Neumann approach, which incorporates open boundaries by introducing an applied bias and a circulating current. The dissipated electromagnetic power can be computed in this context from the time derivative of the energy. This scheme is applied in combination with a self-consistent tight-binding Hamiltonian to investigate the effects of bias and molecular size on the electroluminescence of metallic and semiconducting chains. For the latter, a complex interplay between bias and molecular length is observed: there is an optimal number of atoms that maximizes the emitted power at high voltages but not at low ones. This unanticipated behavior can be understood in terms of the band bending produced along the semiconducting chain, a phenomenon that is captured by the self-consistency of the method. A simple analytical model is proposed that explains the main features revealed by the simulations. The methodology, applied here at a self-consistent tight-binding level but extendable to more sophisticated Hamiltonians such as density functional tight binding and time dependent density functional theory, promises to be helpful for quantifying the power and quantum efficiency of nanoscale electroluminescent devices. [ABSTRACT FROM AUTHOR]

We develop a quasiparticle approach to capture the dynamics of open quantum systems coupled to bosonic thermal baths of arbitrary complexity based on the Hierarchical Equations of Motion (HEOM). This is done by generalizing the HEOM dynamics and mapping it into that of the system in interaction with a few bosonic fictitious quasiparticles that we call bexcitons. Bexcitons arise from a decomposition of the bath correlation function into discrete features. Specifically, bexciton creation and annihilation couple the auxiliary density matrices in the HEOM. The approach provides a systematic strategy to construct exact quantum master equations that include the system–bath coupling to all orders even for non-Markovian environments. Specifically, by introducing different metrics and representations for the bexcitons it is possible to straightforwardly generate different variants of the HEOM, demonstrating that all these variants share a common underlying quasiparticle picture. Bexcitonic properties, while unphysical, offer a coarse-grained view of the correlated system–bath dynamics and its numerical convergence. For instance, we use it to analyze the instability of the HEOM when the bath is composed of underdamped oscillators and show that it leads to the creation of highly excited bexcitons. The bexcitonic picture can also be used to develop more efficient approaches to propagate the HEOM. As an example, we use the particle-like nature of the bexcitons to introduce mode-combination of bexcitons in both number and coordinate representation that uses the multi-configuration time-dependent Hartree to efficiently propagate the HEOM dynamics. [ABSTRACT FROM AUTHOR]

The time-dependent quantum transportation through a metal/polymer/metal system is theoretically investigated on the basis of a Su–Schrieffer–Heeger model combined with the hierarchical equations of motion formalism. Using a non-adiabatic dynamical method, the evolution of the electron subspace and lattice atoms with time can be obtained. It is found that the calculated transient currents vary with time and reach stable values after a response time under the bias voltages. However, the stable current as the system reaches its dynamical steady state exhibits a discrepancy between two sweep directions of the bias voltage, which results in pronounced electrical hysteresis loops in the current–voltage curve. By analyzing the evolution of instantaneous energy eigenstates, the occupation number of the instantaneous eigenstates, and the lattice of the polymer, we show that the formation of excitons and the delay of their annihilation are responsible for the hysteretic current–voltage characteristics, where electron–phonon interactions play the key factor. Furthermore, the hysteresis width and amplitude can also be modulated by the strength of the electron–phonon coupling, level-width broadening function, and temperature. We hope these results about past condition-dependent switching performance at a sweep voltage can provide further insight into some of the basic issues of interest in hysteresis processes in conducting polymers. [ABSTRACT FROM AUTHOR]

A novel mixed quantum–classical approach to simulating nonadiabatic dynamics of molecules at metal surfaces is presented. The method combines the numerically exact hierarchical equations of motion approach for the quantum electronic degrees of freedom with Langevin dynamics for the classical degrees of freedom, namely, low-frequency vibrational modes within the molecule. The approach extends previous mixed quantum–classical methods based on Langevin equations to models containing strong electron–electron or quantum electronic–vibrational interactions, while maintaining a nonperturbative and non-Markovian treatment of the molecule–metal coupling. To demonstrate the approach, nonequilibrium transport observables are calculated for a molecular nanojunction containing strong interactions. [ABSTRACT FROM AUTHOR]

A time-dependent vibrational electronic coupled-cluster (VECC) approach is proposed to simulate photo-electron/UV-VIS absorption spectra as well as time-dependent properties for non-adiabatic vibronic models, going beyond the Born–Oppenheimer approximation. A detailed derivation of the equations of motion and a motivation for the ansatz are presented. The VECC method employs second-quantized bosonic construction operators and a mixed linear and exponential ansatz to form a compact representation of the time-dependent wave-function. Importantly, the method does not require a basis set, has only a few user-defined inputs, and has a classical (polynomial) scaling with respect to the number of degrees of freedom (of the vibronic model), resulting in a favorable computational cost. In benchmark applications to small models and molecules, the VECC method provides accurate results compared to multi-configurational time-dependent Hartree calculations when predicting short-time dynamical properties (i.e., photo-electron/UV–VIS absorption spectra) for non-adiabatic vibronic models. To illustrate the capabilities, the VECC method is also successfully applied to a large vibronic model for hexahelicene with 14 electronic states and 63 normal modes, developed in the group by Aranda and Santoro [J. Chem. Theory Comput. 17, 1691, (2021)]. [ABSTRACT FROM AUTHOR]

Controlling molecular reactivity by shaped laser pulses is a long-standing goal in chemistry. Here, we suggest a direct optimal control approach that combines external pulse optimization with other control parameters arising in the upcoming field of vibro-polaritonic chemistry for enhanced controllability. The direct optimal control approach is characterized by a simultaneous simulation and optimization paradigm, meaning that the equations of motion are discretized and converted into a set of holonomic constraints for a nonlinear optimization problem given by the control functional. Compared with indirect optimal control, this procedure offers great flexibility, such as final time or Hamiltonian parameter optimization. A simultaneous direct optimal control theory will be applied to a model system describing H-atom transfer in a lossy Fabry–Pérot cavity under vibrational strong coupling conditions. Specifically, optimization of the cavity coupling strength and, thus, of the control landscape will be demonstrated. [ABSTRACT FROM AUTHOR]

The operations of current quantum computers are still significantly affected by decoherence caused by interaction with the environment. In this work, we employ the non-perturbative hierarchical equations of motion (HEOM) method to simulate the operation of model quantum computers and reveal the effects of dissipation on the entangled quantum states and on the performance of well-known quantum algorithms. Multi-qubit entangled states in Shor's factorizing algorithm are first generated and propagated using the HEOM. It is found that the failure of factorization is accompanied by a loss of fidelity and mutual information. An important challenge in using the HEOM to simulate quantum computers in a dissipative environment is how to efficiently treat systems with many qubits. We propose a two-dimensional tensor network scheme for this problem and demonstrate its capability by simulating a one-dimensional random circuit model with 21 qubits. [ABSTRACT FROM AUTHOR]

Scaffolded molecular networks are important building blocks in biological pigment–protein complexes, and DNA nanotechnology allows analogous systems to be designed and synthesized. System–environment interactions in these systems are responsible for important processes, such as the dissipation of heat and quantum information. This study investigates the role of nanoscale molecular parameters in tuning these vibronic system–environment dynamics. Here, genetic algorithm methods are used to obtain nanoscale parameters for a DNA-scaffolded chromophore network based on comparisons between its calculated and measured optical spectra. These parameters include the positions, orientations, and energy level characteristics within the network. This information is then used to compute the dynamics, including the vibronic population dynamics and system–environment heat currents, using the hierarchical equations of motion. The dissipation of quantum information is identified by the system's transient change in entropy, which is proportional to the heat currents according to the second law of thermodynamics. These results indicate that the dissipation of quantum information is highly dependent on the particular nanoscale characteristics of the molecular network, which is a necessary first step before gleaning the systematic optimization rules. Subsequently, the I-concurrence dynamics are calculated to understand the evolution of the vibronic system's quantum entanglement, which are found to be long-lived compared to these system–bath dissipation processes. [ABSTRACT FROM AUTHOR]

A first implementation of analytic gradients for spinor-based relativistic equation-of-motion coupled-cluster singles and doubles method using an exact two-component Hamiltonian augmented with atomic mean-field spin–orbit integrals is reported. To demonstrate its applicability, we present calculations of equilibrium structures and harmonic vibrational frequencies for the electronic ground and excited states of the radium mono-amide molecule (RaNH2) and the radium mono-methoxide molecule (RaOCH3). Spin–orbit coupling is shown to quench Jahn–Teller effects in the first excited state of RaOCH3, resulting in a C3v equilibrium structure. The calculations also show that the radium atoms in these molecules serve as efficient optical cycling centers. [ABSTRACT FROM AUTHOR]

In this work, we formulate the equations of motion corresponding to the Hermitian operator method in the framework of the doubly occupied configuration interaction space. The resulting algorithms turn out to be considerably simpler than the equations provided by that method in more conventional spaces, enabling the determination of excitation energies in N-electron systems under an affordable polynomial computational cost. The implementation of this technique only requires to know the elements of low-order reduced density matrices of an N-electron reference state, which can be obtained from any approximate method. We contrast our procedure against the reduced Bardeen–Cooper–Schrieffer and Richardson–Gaudin–Kitaev integrable models, pointing out the reliability of our proposal. [ABSTRACT FROM AUTHOR]

Interpreting high-dimensional data from molecular dynamics simulations is a persistent challenge. In this paper, we show that for a small peptide, deca-alanine, metastable states can be identified through a neural net based on structural information alone. While processing molecular dynamics data, dimensionality reduction is a necessary step that projects high-dimensional data onto a low-dimensional representation that, ideally, captures the conformational changes in the underlying data. Conventional methods make use of the temporal information contained in trajectories generated through integrating the equations of motion, which forgoes more efficient sampling schemes. We demonstrate that EncoderMap, an autoencoder architecture with an additional distance metric, can find a suitable low-dimensional representation to identify long-lived molecular conformations using exclusively structural information. For deca-alanine, which exhibits several helix-forming pathways, we show that this approach allows us to combine simulations with different biasing forces and yields representations comparable in quality to other established methods. Our results contribute to computational strategies for the rapid automatic exploration of the configuration space of peptides and proteins. [ABSTRACT FROM AUTHOR]

When an activated complex, as defined in transition state theory (TST), has a polyhedral shape, its kinetic energy is found to be diagonal in a system of spherical polar coordinates. If, in addition, the polyhedron is characterized by a high symmetry, then its dynamics considerably simplifies. An application of this approach to the most symmetrical TS known to date, i.e., that which controls the Cl− + CH3Cl → ClCH3 + Cl− SN2 nucleophilic substitution, is presented and an analytical expression of its potential energy surface is provided. In a substantial range around the saddle point, approximate equations of motion for the two components of the reaction coordinate, i.e., the antisymmetrical stretching motion of the ClCCl core and the wagging motion of the hydrogen triad, can be derived in an analytical form. During an extensive period of time, the main component of the reaction coordinate is governed by an unexpectedly simple equation of motion that depends on a single initial condition, irrespective of the other ones and of the internal energy. Reactive trajectories are observed to form a perfectly collimated bundle characterized by undetectable dispersion, thereby giving a spectacular example of regular dynamics in an anharmonic potential. Regularity and collimation are brought about by local symmetry, which is a widespread feature of potential energy surfaces. Anharmonicity is observed to influence the dynamics only at a late stage. As energy increases, trajectories tend to fan out and to deviate from the analytical equation. For the wagging motion, chaos sets in at much lower energies. [ABSTRACT FROM AUTHOR]

Numerically "exact" methods addressing the dynamics of coupled electron–phonon systems have been intensively developed. Nevertheless, the corresponding results for the electron mobility μdc are scarce, even for the one-dimensional (1d) Holstein model. Building on our recent progress on single-particle properties, here we develop the momentum-space hierarchical equations of motion (HEOM) method to evaluate real-time two-particle correlation functions of the 1d Holstein model at a finite temperature. We compute numerically "exact" dynamics of the current–current correlation function up to real times sufficiently long to capture the electron's diffusive motion and provide reliable results for μdc in a wide range of model parameters. In contrast to the smooth ballistic-to-diffusive crossover in the weak-coupling regime, we observe a temporally limited slow-down of the electron on intermediate time scales already in the intermediate-coupling regime, which translates to a finite-frequency peak in the optical response. Our momentum-space formulation lowers the numerical effort with respect to existing HEOM-method implementations, while we remove the numerical instabilities inherent to the undamped-mode HEOM by devising an appropriate hierarchy closing scheme. Still, our HEOM remains unstable at too low temperatures, for too strong electron–phonon coupling, and for too fast phonons. [ABSTRACT FROM AUTHOR]

We present numerically exact quantum dynamics simulations using the hierarchical equation of motion approach to investigate the resonance enhancement of chemical reactions due to the vibrational strong coupling (VSC) in polariton chemistry. The results reveal that the cavity mode acts like a "rate-promoting vibrational mode" that enhances the ground state chemical reaction rate constant when the cavity mode frequency matches the vibrational transition frequency. The exact simulation predicts that the VSC-modified rate constant will change quadratically as the light–matter coupling strength increases. When changing the cavity lifetime from the lossy limit to the lossless limit, the numerically exact results predict that there will be a turnover of the rate constant. Based on the numerical observations, we present an analytic rate theory to explain the observed sharp resonance peak of the rate profile when tuning the cavity frequency to match the quantum transition frequency of the vibrational ground state to excited states. This rate theory further explains the origin of the broadening of the rate profile. The analytic rate theory agrees with the numerical results under the golden rule limit and the short cavity lifetime limit. To the best of our knowledge, this is the first analytic theory that is able to explain the sharp resonance behavior of the VSC-modified rate profile when coupling an adiabatic ground state chemical reaction to the cavity. We envision that both the numerical analysis and the analytic theory will offer invaluable theoretical insights into the fundamental mechanism of the VSC-induced rate constant modifications in polariton chemistry. [ABSTRACT FROM AUTHOR]

Hydrogen atom scattering on metal surfaces is investigated based on a simplified Newns–Anderson model. Both the nuclear and electronic degrees of freedom are treated quantum mechanically. By partitioning all the surface electronic states as the bath, the hierarchical equations of motion method for the fermionic bath is employed to simulate the scattering dynamics. It is found that, with a reasonable set of parameters, the main features of the recent experimental studies of hydrogen atom scattering on metal surfaces can be reproduced. Vibrational states on the chemisorption state whose energies are close to the incident energy are found to play an important role, and the scattering process is dominated by a single-pass electronic transition forth and back between the diabatic physisorption and chemisorption states. Further study on the effects of the atom-surface coupling strength reveals that, upon increasing the atom-surface coupling strength, the scattering mechanism changes from typical nonadiabatic transitions to dynamics in the electronic friction regime. [ABSTRACT FROM AUTHOR]

Simulations of laser-induced electron dynamics in a molecular system are performed using time-dependent (TD) equation-of-motion (EOM) coupled-cluster (CC) theory. The target system has been chosen to highlight potential shortcomings of truncated TD-EOM-CC methods [represented in this work by TD-EOM-CC with single and double excitations (TD-EOM-CCSD)], where unphysical spectroscopic features can emerge. Specifically, we explore driven resonant electronic excitations in magnesium fluoride in the proximity of an avoided crossing. Near the avoided crossing, the CCSD similarity-transformed Hamiltonian is defective, meaning that it has complex eigenvalues, and oscillator strengths may take on negative values. When an external field is applied to drive transitions to states exhibiting these traits, unphysical dynamics are observed. For example, the stationary states that make up the time-dependent state acquire populations that can be negative, exceed one, or even complex-valued. [ABSTRACT FROM AUTHOR]

Current-induced bond rupture is a fundamental process in nanoelectronic architectures, such as molecular junctions, and scanning tunneling microscopy measurements of molecules at surfaces. The understanding of the underlying mechanisms is important for the design of molecular junctions that are stable at higher bias voltages and is a prerequisite for further developments in the field of current-induced chemistry. In this work, we analyze the mechanisms of current-induced bond rupture employing a recently developed method, which combines the hierarchical equations of motion approach in twin space with the matrix product state formalism and allows accurate, fully quantum mechanical simulations of the complex bond rupture dynamics. Extending previous work [Ke et al. J. Chem. Phys. 154, 234702 (2021)], we consider specifically the effect of multiple electronic states and multiple vibrational modes. The results obtained for a series of models of increasing complexity show the importance of vibronic coupling between different electronic states of the charged molecule, which can enhance the dissociation rate at low bias voltages profoundly. [ABSTRACT FROM AUTHOR]

We present a time-dependent variational method to learn the mechanisms of equilibrium reactive processes and efficiently evaluate their rates within a transition path ensemble. This approach builds off of the variational path sampling methodology by approximating the time-dependent commitment probability within a neural network ansatz. The reaction mechanisms inferred through this approach are elucidated by a novel decomposition of the rate in terms of the components of a stochastic path action conditioned on a transition. This decomposition affords an ability to resolve the typical contribution of each reactive mode and their couplings to the rare event. The associated rate evaluation is variational and systematically improvable through the development of a cumulant expansion. We demonstrate this method in both over- and under-damped stochastic equations of motion, in low-dimensional model systems, and in the isomerization of a solvated alanine dipeptide. In all examples, we find that we can obtain quantitatively accurate estimates of the rates of the reactive events with minimal trajectory statistics and gain unique insights into transitions through the analysis of their commitment probability. [ABSTRACT FROM AUTHOR]

In this work, we investigate the multimode Brownian oscillators in nonequilibrium scenarios with multiple reservoirs at different temperatures. For this purpose, an algebraic method is proposed. This approach gives the exact time-local equation of motion for the reduced density operator, from which we can easily extract not only the reduced system but also hybrid bath dynamical information. The resulting steady-state heat current is found to be numerically consistent with another discrete imaginary-frequency method followed by Meir–Wingreen's formula. It is anticipated that the development in this work would constitute an indispensable component of nonequilibrium statistical mechanics for open quantum systems. [ABSTRACT FROM AUTHOR]

In this paper, we present an extended dissipaton equation of motion for studying the dynamics of electronic impurity systems. Compared with the original theoretical formalism, the quadratic couplings are introduced into the Hamiltonian accounting for the interaction between the impurity and its surrounding environment. By exploiting the quadratic fermionic dissipaton algebra, the proposed extended dissipaton equation of motion offers a powerful tool for studying the dynamical behaviors of electronic impurity systems, particularly in situations where nonequilibrium and strongly correlated effects play significant roles. Numerical demonstrations are carried out to investigate the temperature dependence of the Kondo resonance in the Kondo impurity model. [ABSTRACT FROM AUTHOR]

Many approximate solutions of the time-dependent Schrödinger equation can be formulated as exact solutions of a nonlinear Schrödinger equation with an effective Hamiltonian operator depending on the state of the system. We show that Heller's thawed Gaussian approximation, Coalson and Karplus's variational Gaussian approximation, and other Gaussian wavepacket dynamics methods fit into this framework if the effective potential is a quadratic polynomial with state-dependent coefficients. We study such a nonlinear Schrödinger equation in full generality: we derive general equations of motion for the Gaussian's parameters, demonstrate time reversibility and norm conservation, and analyze conservation of energy, effective energy, and symplectic structure. We also describe efficient, high-order geometric integrators for the numerical solution of this nonlinear Schrödinger equation. The general theory is illustrated by examples of this family of Gaussian wavepacket dynamics, including the variational and nonvariational thawed and frozen Gaussian approximations and their special limits based on the global harmonic, local harmonic, single-Hessian, local cubic, and local quartic approximations for the potential energy. We also propose a new method by augmenting the local cubic approximation with a single fourth derivative. Without substantially increasing the cost, the proposed "single-quartic" variational Gaussian approximation improves the accuracy over the local cubic approximation and, at the same time, conserves both the effective energy and symplectic structure, unlike the much more expensive local quartic approximation. Most results are presented in both Heller's and Hagedorn's parametrizations of the Gaussian wavepacket. [ABSTRACT FROM AUTHOR]

In this paper, we study Little Rip (LR) and Pseudo Rip (PR) cosmological models containing two coupled fluids: dark energy and dark matter. We assume a spatially flat Friedmann–Robertson–Walker (FRW) universe. The interaction between the dark energy and the dark matter fluid components is described in terms of the parameters in the generalized Equation of State (EoS) in presence of the bulk viscosity. We consider entropic cosmology and use a description based on a new generalized entropy function, which was proposed by Nojiri–Odintsov–Faraoni [From nonextensive statistics and black hole entropy to the holographic dark universe, Phys. Rev. D105(4) (2022) 044042]. Conditions for the appearance of the (LR) and the (PR) in terms of the parameters of the (EoS) are obtained. Introducing an energy density ρ g corresponding to a specified entropy function S g , together with an interaction term Q in the gravitational equations of motion, we derive modified forms of the EoS parameters. We discuss the corrections of the thermodynamic parameters associated with the generalized entropy function. Properties of the late universe as well as in the early universe in this formalism are pointed out. [ABSTRACT FROM AUTHOR]

The utilization of functionally graded graphene platelet-reinforced composites (FG-GPLRC) and honeycomb sandwich constructions is prevalent in the field of engineering. Therefore, it is crucial to investigate the buckling and vibration properties of these materials under heat circumstances. This paper specifically focuses on the vibration and thermal buckling characteristics of a novel multi-arc concave honeycomb sandwich plate (MACHSP) equipped with an adjustable positive-negative Poisson's ratio. The governing equations of motion for the system are derived based on the first-order shear deformation theory in conjunction with Hamilton's principle. The formulation of the system's characteristic equation involves the establishment of displacement functions that satisfy distinct boundary conditions. Using computational programming, natural frequencies, mode shapes, and critical buckling temperatures of MACHSP with three different FG-GPLRC distributions under thermal influences are determined. Subsequently, these results are compared with outcomes from finite element simulations and findings from previously published literature. Additionally, the amplitude-frequency response characteristics of the structure under harmonic excitation are analyzed, followed by a discussion of the impact of structural parameters on its buckling and vibration characteristics. The results indicate that the established theoretical model for predicting the buckling and vibration characteristics of MACHSP with FG-GPLRC distribution aligns well with simulation models and prior research. In contrast to solid plates, MACHSP not only achieves a substantial reduction in weight but also demonstrates a significant increase in natural frequency. Furthermore, graphene platelets have the potential to enhance the structure's natural frequency values and critical buckling temperatures. Lastly, various structural parameters exert a notable influence on the structure's performance. [ABSTRACT FROM AUTHOR]

A proper understanding of excited state properties of indole derivatives can lead to rational design of efficient fluorescent probes. The optically active La$$ {L}_a $$ and Lb$$ {L}_b $$ excited states of a series of substituted indoles, where a substituent was placed on position four, were calculated using equation of motion coupled cluster and time dependent density functional theory. The results indicate that most substituted indoles have a brighter second excited state corresponding to experimental absorption maxima, but a few with electron withdrawing substituents absorb more on the first excited state. Absorption on the first excited state may increase their fluorescence quantum yield, making them better probes. Electronic structure methods were found to predict the energies of the systems with electron withdrawing substituents more accurately than those with electron donating substituents. The excited states of both states correlated well with electrophilicity, similar to the experimental trends for the absorption maxima. Overall, these computational studies indicate that theory can be used to predict excited state properties of substituted indoles, when the substituent is an electron withdrawing group. [ABSTRACT FROM AUTHOR]

Data‐driven structural health monitoring (SHM) is an approach which relies on the information contained in the data and through signal analysis techniques captures the features, variations, and uncertainties that data contain. This paper presents the response of shaking table tests of a full‐scale, 3‐story building with sliding slabs connected by horizontal buckling‐restrained braces for energy dissipation. First, the global dynamic characteristics of the structure were identified from a series of the building response data under different intensity level of base excitations. The variation of the identified modal parameters, such as the mode frequencies and modal shapes, was discovered. The influence of sliding slabs on the dynamic characteristics of the frame was also investigated through the measured response and the equation of motion with six degree of freedom systems. Comparison on the achieved interstory stiffness due to the implementation of sliding slabs and the fixed (locked up) slab was examined. The mechanism and dynamic characteristics of sliding slabs, including energy dissipation of the friction force, BRB hysteresis behavior, and unintended damping force during strong base excitation were analyzed directly using the ARX/recursive model. The extracted unintended damping force performed like a friction hysteretic response, which needs to be considered for frame modeling in shaking table tests. The findings through the data analysis have clarified the important aspects of sliding slabs and demonstrated the benefits and applicability of sliding slabs on reducing the frame response. [ABSTRACT FROM AUTHOR]

In molten metals, the atomic dynamics have been studied in the present study with the help of equations of motion in terms of the velocity autocorrelation function (VACF), power spectrum $ G(\omega) $ G (ω) , and mean square displacement $ {r^2}(t) $ r 2 (t). The pair correlation function $ g(r) $ g (r) is used to produce VACF for molten metals in the current study with the help of three different types of structure factor methods i.e. hard sphere Yukawa (HSY) method, optimised random phase approximation (ORPA) method and charged hard sphere (CHS) method. The presently obtained results for molten metals of different groups like Na (Z = 1), Mg (Z = 2), Al (Z = 3), Sn (Z = 4), and Sb (Z = 5) are compared with the molecular dynamic (MD) study and also with the other theoretical data available in the literature. For the present study, our own developed pseudopotential has been used for the calculations of the above-mentioned properties. The screening effect is also been observed over and beyond the bare ion potential with Hartree (H) and the effects of exchanges and correlation were computed using procedures given by Taylor (T) and Nagy (N). [ABSTRACT FROM AUTHOR]

In this paper, we explore some cosmological solutions of the Friedmann–Lemaître–Robertson–Walker (FLRW) closed universe with nonlocal de Sitter gravity d S and nonlocal scalar field which has its origin in p -adic string theory. In this case, we have that both geometrical and matter sectors of equations of motion (EoM) are nonlocal. The cosmological constant Λ plays a role of dark energy (DE) and is related to the mass of scalar field as m = ℏ c Λ 6 = 1. 5 × 1 0 − 6 9 kg. We found that the cosmological constant Λ depends on prime number p as a discrete parameter and we conjectured that Λ is not constant during the universe evolution. [ABSTRACT FROM AUTHOR]

A relativistic version of the correspondence principle, a limit in which classical electrodynamics may be derived from quantum electrodynamics (QED), has never been clear, especially when including gravitational mass. Here we introduce a novel classical field theory formulation of electromagnetism, and then show that it approximates QED in the limit of a quantum state which corresponds to a classical charged continua. Our formulation of electromagnetism features a Lagrangian which is gauge invariant, includes a classical complex field from which a divergenceless four-current may be derived, and reproduces all aspects of the classical theory of charged massive continua without any quantum effects. Taking a geometric approach, we identify the four-current as being in the direction of extremal phase velocity of the classical field; the field equations of motion determine this phase velocity as being equal to the mass, which makes the rest density proportional to the squared modulus of the field. [ABSTRACT FROM AUTHOR]

In this study, we investigate the behavior of the Dirac–Born–Infeld (DBI) scalar field as a candidate for the nature of dark energy in a non-minimal coupling scenario with the scalar torsion within the framework of teleparallel gravity. We present numerical solutions for the equations of motion and analyze the behavior of various cosmological parameters for different values of the parameter ṽ and f̃. Our findings reveal that the DBI scalar field can contribute significantly to the energy density of the universe and drive the late-time acceleration of the universe, with a transition from deceleration to acceleration occurring within a redshift range consistent with recent observational bounds. We show that the present-day value of the deceleration parameter is consistent with recent observational constraints, and the DBI scalar field behaves like a cosmological constant model. Our results suggest that the DBI scalar field can play a significant role in driving the late-time acceleration of the universe and that it has the potential to be a viable alternative to the cosmological constant model. Further investigations are necessary to better understand the nature of the dark energy component and its implications for cosmology within the framework of teleparallel gravity. [ABSTRACT FROM AUTHOR]

An inerter system, based on electromechanical similarity theory and vibration mitigation and isolation technology, represents a category of vibration damping systems. These systems typically improve damping performance by increasing mass or inertia, a method often found to be inefficient, leading to inadequate damping and limited applicability in real-world engineering scenarios. The lightweight inerter system (LwIS) introduced herein offers a more flexible and efficient means of altering structural inertia. Initially, this paper establishes the motion control equations for LwIS, followed by a stochastic analysis to derive the analytical expression for the root mean square displacement under Gaussian white noise excitation. A parametric analysis of LwIS is subsequently conducted, developing a displacement-based parametric strategy. Design examples for single-degree-of-freedom (SDOF) engineering structures under various requirements are provided, demonstrating the validity of LwIS’s optimal parameters through responses to simple harmonic excitation and seismic impacts. The findings indicate that the optimization approach of LwIS, unlike traditional methods, simultaneously addresses the displacement performance of the primary structure and the deformation efficiency of the damping element, thereby facilitating comprehensive optimization. Four optimal design parameters for LwIS are identified, underscoring its applicability to stochastic excitation and a broader range of load cases, thus enhancing its practicality in engineering contexts. LwIS’s design philosophy aims to improve deformation efficiency through an increased deformation enhancement coefficient in the damping element, enhancing damping performance, controlling seismic responses, and achieving superior energy dissipation. The optimal parameters, smaller in value, maximize the potential of the inerter system, aligning with the dual objectives of performance optimization and lightweight design, consequently reducing engineering costs. [ABSTRACT FROM AUTHOR]

This paper seeks to study and investigate the wave dispersion behavior in porous functionally graded (FG) carbon nanotube-reinforced composite (CNTRC) beams. The beams comprise four patterns of single-walled carbon nanotubes (SWCNTs) distributed in the polymer matrix. The mixture rule is used to estimate the CNTR beams’ material properties. Innovative to this study are three porosity models describing the porosity distributions within the matrix and a three-unknown integral higher-order shear deformation theory (HSDT) modeling analytically the CNTRC beams with a novel shape function expressing the distributions of shear stresses and strains. The equations of motion for CNTRC beams are derived based on Hamilton’s principle. The stiffness and mass matrices are formulated by a generalized solution of harmonic wave propagation to express the wave dispersion relations. Numerical comparisons with previously published works verify the applicability of this mathematical model. The paper studies the effects of CNTs patterns through the polymer matrix, porosity models, and volume fractions of the porosity and CNTs. Based on the analytical results, augmenting the porosity and CNTs volume fractions leads to faster phase and group velocities. Furthermore, the impact of CNTs volume fractions, porosity models, and porosity volume fractions becomes more pronounced as the wavenumber increases. [ABSTRACT FROM AUTHOR]

General Relativity describes the trajectories of light-rays through curved spacetime near a massive object. In addition to gravitational lensing, we include an absorbing dielectric medium given by a complex refractive index known as the Drude model. When absorption is included the eikonal becomes complex, with the imaginary part related to the absorption along a ray between emission and observation points. We extend results from the literature to include dispersion in the index of refraction. The complex Hamiltonian splits into a real part that describes the equations of motion and a constraint equation that governs the momentum loss in the system. We work in coordinates which are fully real, with a real metric in physical spacetime. We assume the dust and plasma distributions of the Drude matter to coincide and vary as a power-law 1 / r h . We find that transmission requires h > 1, otherwise exponential absorption occurs along ray paths. We use ray-tracing through strongly absorbing matter near the surface of the compact star, as well as specializing to a point-lens in the weak-field limit with weakly absorbing matter to generate potentially observable light curves for distant observers. In the appropriate limits, our theory reproduces results from the literature. [ABSTRACT FROM AUTHOR]

In this article, we consider the equations of motion for an articulated n$$ n $$‐trailer vehicle with different masses and inertias in the presence of force and torque commands. We design a second‐order optimal filter to estimate the pose of the first vehicle and of the trailers exploiting the Lie group structure and the nonholonomic and hooking constraints. We consider the filtering problem from three different perspectives: in the first masses and inertias are time‐varying and perfectively known, in the second they are known only in the first part of the maneuver, but they are not updated over time. In the last case masses and inertias are considered within the state vector and therefore estimated by the filter. Depending on the needs in real‐life applications (e.g., whether the masses and inertias remain fixed or change during the maneuver and are unknown), the best‐performing filter can be used. The sensing system consists of a GPS‐like configuration (global positioning system) obtained by using an antenna attached to the leading car. [ABSTRACT FROM AUTHOR]

This paper is concerned with the modeling and mathematical analysis of linear peridynamic model for arbitrary Poisson ratio's material. Based on the fundamental laws of dynamics, we re‐derive the bond‐based peridynamic model for anisotropic materials by relaxing certain assumptions. Through this process, we draw several significant conclusions, such as the relationship between the equivalent strain energy density hypothesis and the convergence of the peridynamic operator to the classical Navier operator. Additionally, the well‐posedness of time‐dependent peridynamic equations of motion is established. Finally, some necessary conditions for the material stability of anisotropic material are given. [ABSTRACT FROM AUTHOR]