Search

A generalised time reversal symmetry for systems subject to a constant magnetic field is introduced, based on the analogy between the evolution equations of these systems and those of a system subject to shear. This generalisation makes it possible to derive symmetry relations for time correlation functions that do not require to change the sign of the magnetic field upon time reversal. This is to be contrasted with the standard Kubo result in which the sign of the magnetic field does change, thus establishing a symmetry relation between two distinct physical situations. Our result implies, for example, that Onsager-Casimir relations may be replaced by Onsager reciprocal relations even in the presence of a constant magnetic field. It is also of practical importance to interpret experiments and numerical simulations in which the systems considered are in a single magnetic field. [ABSTRACT FROM AUTHOR]

The Open Databases Integration for Materials Design (OPTIMADE) application programming interface (API) empowers users with holistic access to a growing federation of databases, enhancing the accessibility and discoverability of materials and chemical data. Since the first release of the OPTIMADE specification (v1.0), the API has undergone significant development, leading to the v1.2 release, and has underpinned multiple scientific studies. In this work, we highlight the latest features of the API format, accompanying software tools, and provide an update on the implementation of OPTIMADE in contributing materials databases. We end by providing several use cases that demonstrate the utility of the OPTIMADE API in materials research that continue to drive its ongoing development., Competing Interests: G. J. C. is a shareholder and Director of Intellegens Ltd. G.-M. R. is a shareholder and Chief Innovation Officer of Matgenix SRL. E. B. is a shareholder and Director of Materials Platform for Data Science OÜ., (This journal is © The Royal Society of Chemistry.)

Rare events include many of the most interesting transformation processes in condensed matter, from phase transitions to biomolecular conformational changes to chemical reactions. Access to the corresponding mechanisms, free-energy landscapes and kinetic rates can in principle be obtained by different techniques after projecting the high-dimensional atomic dynamics on one (or a few) collective variable. Even though it is well-known that the projected dynamics approximately follows - in a statistical sense - the generalized, underdamped or overdamped Langevin equations (depending on the time resolution), to date it is nontrivial to parameterize such equations starting from a limited, practically accessible amount of non-ergodic trajectories. In this work we focus on Markovian, underdamped Langevin equations, that arise naturally when considering, e.g., numerous water-solution processes at sub-picosecond resolution. After contrasting the advantages and pitfalls of different numerical approaches, we present an efficient parametrization strategy based on a limited set of molecular dynamics data, including equilibrium trajectories confined to minima and few hundreds transition path sampling-like trajectories. Employing velocity autocorrelation or memory kernel information for learning the friction and likelihood maximization for learning the free-energy landscape, we demonstrate the possibility to reconstruct accurate barriers and rates both for a benchmark system and for the interaction of carbon nanoparticles in water., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

A new algorithm for efficient and fully time-reversible integration of first-principles molecular dynamics based on orbital-free density functional theory (OFDFT) is presented. The algorithm adapts to this nontrivial case, the recently introduced Mass-Zero (MaZe) constrained dynamics. The formalism ensures that full adiabatic separation is enforced between nuclear and electronic degrees of freedom and, consequently, that the exact Born-Oppenheimer probability for the nuclei is sampled. Numerical integration of the MaZe dynamics combines standard molecular dynamics algorithms, e.g., Verlet or velocity Verlet, with the SHAKE method to impose the minimum conditions on the electronic degrees of freedom as a set of constraints. The developments presented in this work, which include a bespoke adaptation of the standard SHAKE algorithm, ensure that the quasilinear scaling of OFDFT is preserved by the new method for a broad range of kinetic and exchange-correlation functionals, including nonlocal ones. The efficiency and accuracy of the approach are demonstrated via calculations of static and dynamic properties of liquid sodium in the constant energy and constant temperature ensembles.

Electrochemistry is central to many applications, ranging from biology to energy science. Studies now involve a wide range of techniques, both experimental and theoretical. Modeling and simulations methods, such as density functional theory or molecular dynamics, provide key information on the structural and dynamic properties of the systems. Of particular importance are polarization effects of the electrode/electrolyte interface, which are difficult to simulate accurately. Here, we show how these electrostatic interactions are taken into account in the framework of the Ewald summation method. We discuss, in particular, the formal setup for calculations that enforce periodic boundary conditions in two directions, a geometry that more closely reflects the characteristics of typical electrolyte/electrode systems and presents some differences with respect to the more common case of periodic boundary conditions in three dimensions. These formal developments are implemented and tested in MetalWalls, a molecular dynamics software that captures the polarization of the electrolyte and allows the simulation of electrodes maintained at a constant potential. We also discuss the technical aspects involved in the calculation of two sets of coupled degrees of freedom, namely the induced dipoles and the electrode charges. We validate the implementation, first on simple systems, then on the well-known interface between graphite electrodes and a room-temperature ionic liquid. We finally illustrate the capabilities of MetalWalls by studying the adsorption of a complex functionalized electrolyte on a graphite electrode.

The performance of different approximate algorithms for computing anharmonic features in vibrational spectra is analyzed and compared on model and more realistic systems that present relevant nuclear quantum effects. The methods considered combine approximate sampling of the quantum thermal distribution with classical time propagation and include Matsubara dynamics, path integral dynamics approaches, linearized initial value representation, and the recently introduced adaptive quantum thermal bath. A perturbative analysis of these different methods enables us to account for the observed numerical performance on prototypes for overtones and combination bands and to draw qualitatively correct trends for the numerical results obtained for Fermi resonances. Our results prove that the unequal performances of these approaches often derive from the method employed to sample initial conditions and not, as usually assumed, from the lack of coherence in the time propagation. Furthermore, as confirmed by the analysis reported in Benson and Althorpe, J. Chem. Phys. 130, 194510 (2021), we demonstrate, both via the perturbative approach and numerically, that path integral dynamics methods fail to reproduce the intensities of these anharmonic features and follow purely classical trends with respect to their temperature behavior. Finally, the remarkably accurate performance of the adaptive quantum thermal bath approach is documented and motivated.

We demonstrate the accuracy and efficiency of a recently introduced approach to account for nuclear quantum effects (NQEs) in molecular simulations: the adaptive quantum thermal bath (adQTB). In this method, zero-point energy is introduced through a generalized Langevin thermostat designed to precisely enforce the quantum fluctuation-dissipation theorem. We propose a refined adQTB algorithm with improved accuracy and report adQTB simulations of liquid water. Through extensive comparison with reference path integral calculations, we demonstrate that it provides excellent accuracy for a broad range of structural and thermodynamic observables as well as infrared vibrational spectra. The adQTB has a computational cost comparable to that of classical molecular dynamics, enabling simulations of up to millions of degrees of freedom.

We illustrate how, contrary to common belief, transient Fluctuation Relations (FRs) for systems in constant external magnetic field hold without the inversion of the field. Building on previous work providing generalized time-reversal symmetries for systems in parallel external magnetic and electric fields, we observe that the standard proof of these important nonequilibrium properties can be fully reinstated in the presence of net dissipation. This generalizes recent results for the FRs in orthogonal fields-an interesting but less commonly investigated geometry-and enables direct comparison with existing literature. We also present for the first time a numerical demonstration of the validity of the transient FRs with nonzero magnetic field via nonequilibrium molecular dynamics simulations of a realistic model of liquid NaCl.

The validity of the fluctuation relations (FRs) for systems in a constant magnetic field is investigated. Recently introduced time-reversal symmetries that hold in the presence of static electric and magnetic fields and of deterministic thermostats are used to prove the transient FRs without invoking, as commonly done, inversion of the magnetic field. Steady-state FRs are also derived, under the t-mixing condition. These results extend the predictive power of important statistical mechanics relations. We illustrate this via the nonlinear response for the cumulants of the dissipation, showing how the alternative FRs enable one to determine analytically null cumulants also for systems in a single magnetic field.

Classical molecular dynamics simulations have recently become a standard tool for the study of electrochemical systems. State-of-the-art approaches represent the electrodes as perfect conductors, modeling their responses to the charge distribution of electrolytes via the so-called fluctuating charge model. These fluctuating charges are additional degrees of freedom that, in a Born-Oppenheimer spirit, adapt instantaneously to changes in the environment to keep each electrode at a constant potential. Here, we show that this model can be treated in the framework of constrained molecular dynamics, leading to a symplectic and time-reversible algorithm for the evolution of all the degrees of freedom of the system. The computational cost and the accuracy of the new method are similar to current alternative implementations of the model. The advantage lies in the accuracy and long term stability guaranteed by the formal properties of the algorithm and in the possibility to systematically introduce additional kinematic conditions of arbitrary number and form. We illustrate the performance of the constrained dynamics approach by enforcing the electroneutrality of the electrodes in a simple capacitor consisting of two graphite electrodes separated by a slab of liquid water.

In recent work [Coretti et al., J. Chem. Phys., 2018, 149, 191102], a new algorithm to solve numerically the dynamics of the shell model for polarization was presented. The approach, broadly applicable to systems involving adiabatically separated dynamical variables, employs constrained molecular dynamics to strictly enforce the condition that the force on the fast degrees of freedom, modeled as having zero mass, is null at each time step. The algorithm is symplectic and fully time reversible, and results in stable and efficient propagation. In this paper we complete the discussion of the mechanics of mass-zero constrained dynamics by showing how to adapt it to problems where the fast degrees of freedom must satisfy additional conditions. This extension includes, in particular, the important case of first principles molecular dynamics. We then consider the statistical mechanics of the mass-zero constrained dynamical system demonstrating that the marginal probability sampled by the dynamics in the physical phase space recovers the form of the Born-Oppenheimer probability density. The effectiveness of the approach and the favorable scaling of the algorithm with system size are illustrated in test calculations of solid Na via orbital-free density functional dynamics.

We revisit the statistical mechanics of charge fluctuations in capacitors. In constant-potential classical molecular simulations, the atomic charges of electrode atoms are treated as additional degrees of freedom which evolve in time so as to satisfy the constraint of fixed electrostatic potential for each configuration of the electrolyte. The present work clarifies the role of the overall electroneutrality constraint, as well as the link between the averages computed within the Born-Oppenheimer approximation and that of the full constant-potential ensemble. This allows us in particular to derive a complete fluctuation-dissipation relation for the differential capacitance, that includes a contribution from the charge fluctuations (around the charges satisfying the constant-potential and electroneutrality constraints) also present in the absence of an electrolyte. We provide a simple expression for this contribution from the elements of the inverse of the matrix defining the quadratic form of the fluctuating charges in the energy. We then illustrate numerically the validity of our results, and recover the expected continuum result for an empty capacitor with structureless electrodes at large inter-electrode distances. By considering a variety of liquids between graphite electrodes, we confirm that this contribution to the total differential capacitance is small compared to that induced by the thermal fluctuations of the electrolyte.

The Wigner thermal density is a function of considerable interest in the area of approximate (linearized or semiclassical) quantum dynamics where it is employed to generate initial conditions for the propagation of appropriate sets of classical trajectories. In this paper, we propose an original approach to compute the Wigner density based on a generalized Langevin equation. The stochastic dynamics is nontrivial in that it contains a coordinate-dependent friction coefficient and a generalized force that couples momenta and coordinates. These quantities are, in general, not known analytically and have to be estimated via auxiliary calculations. The performance of the new sampling scheme is tested on standard model systems with highly nonclassical features such as relevant zero point energy effects, correlation between momenta and coordinates, and negative parts of the Wigner density. In its current brute force implementation, the algorithm, whose convergence can be systematically checked, is accurate and has only limited overhead compared to schemes with similar characteristics. We briefly discuss potential ways to further improve its numerical efficiency.

Quantum thermal bath (QTB) simulations reproduce statistical nuclear quantum effects via a Langevin equation with a colored random force. Although this approach has proven efficient for a variety of chemical and condensed-matter problems, the QTB, as many other semiclassical methods, suffers from zero-point energy leakage (ZPEL). The absence of a reliable criterion to quantify the ZPEL without resorting to demanding comparisons with path integral-based calculations has so far hindered the use of the QTB for the simulation of real systems. In this work, we establish a quantitative connection between ZPEL in the QTB framework and deviations from the quantum fluctuation-dissipation theorem (FDT) that can be monitored along the simulation. This provides a rigorous general criterion to detect and quantify the ZPEL without any a priori knowledge of the system under study. We then use this criterion to build an adaptive QTB method that strictly enforces the quantum FDT at all frequencies via an on-the-fly, spectrally resolved fine-tuning of the system-bath coupling coefficients. The validity of the adaptive approach is first demonstrated on a simple two-oscillator model. It is then applied to two more realistic problems: the description of the vibrational properties of a model aluminum crystal at low temperature and the simulation of the liquid-solid phase transition in a 13-atom neon cluster. In both systems, the standard QTB results are strongly altered by the ZPEL, which can be essentially eliminated using the adaptive approach.

A new algorithm to solve numerically the evolution of empirical shell models of polarizable systems is presented. It employs constrained molecular dynamics to satisfy exactly, at each time step, the crucial condition that the gradient of the potential with respect to the shell degrees of freedom is null. The algorithm is efficient, stable, and, contrary to the available alternatives, it is symplectic and time reversible. A proof-of-principle calculation on a polarizable model for NaCl is presented to illustrate its properties in comparison with the current method, which employs a conjugate-gradient procedure to enforce the null gradient condition. The proposed algorithm is applicable to other cases where a minimum condition on a function of an auxiliary set of driven dynamical variables must be satisfied.

Equilibrium and nonequilibrium molecular dynamics simulations are combined to compute the full set of coefficients that appear in the phenomenological equations describing thermal transport in a binary mixture subject to a constant thermal gradient. The Dynamical Non-Equilibrium Molecular Dynamics approach (D-NEMD) is employed to obtain the microscopic time evolution of the density and temperature fields, together with that of the mass and energy fluxes. D-NEMD enables one to study not only the steady state, but also the evolution of the fields during the transient that follows the onset of the thermal gradient, up to the establishment of the steady state. This makes it possible to ensure that the system has indeed reached a stationary condition, and to analyze the transient mechanisms and time scales of the mass and energy transport. A local time averaging procedure is applied to each trajectory contributing to the calculation to improve the signal-to-noise ratio in the estimation of the fluxes and to obtain a clear signal with the, relatively limited, statistics available.

The time-reversal properties of charged systems in a constant external magnetic field are reconsidered in this paper. We show that the evolution equations of the system are invariant under a new symmetry operation that implies a new signature property for time-correlation functions under time reversal. We then show how these findings can be combined with a previously identified symmetry to determine, for example, null components of the correlation functions of velocities and currents and of the associated transport coefficients. These theoretical predictions are illustrated by molecular dynamics simulations of superionic AgI.

We present a detailed study of the excited state properties of 5-benzyluracil (5BU) in the gas phase and in implicit solvent using different electronic structure approaches ranging from time-dependent density functional theory in the linear response regime (LR-TDDFT) to a set of different wave-function-based methods for excited states, namely perturbed coupled cluster (CC2), algebraic diagrammatic construction method to second order (ADC(2)), and perturbed configuration interaction (CIS(D)). 5BU has been used to investigate DNA base-amino acid interactions. In particular, it served as a model of protein-DNA photoinduced cross-linking. While LR-TDDFT is computationally the most efficient first-principles approach for static and dynamic simulations of this bichromophoric system, its accuracy is difficult to assess due to the presence of excited states with charge transfer character. In this work, the performance of different exchange correlation functionals is compared against accurate benchmarks obtained either from high level wave-function-based methods or directly from experimental absorption spectra. Our investigation shows that accurate results for the excitation energies can be obtained using the hybrid meta-GGA functional M06. In view of dynamical studies of the relaxation of 5BU after photoexcitation, we also show that the PBE functional, while failing in the Franck-Condon region, provides qualitatively good results for the characterisation of a possible photocyclization path.

Vibrational spectroscopy is a fundamental tool to investigate local atomic arrangements and the effect of the environment, provided that the spectral features can be correctly assigned. This can be challenging in experiments and simulations when double peaks are present because they can have different origins. Fermi dyads are a common class of such doublets, stemming from the resonance of the fundamental excitation of a mode with the overtone of another. We present a new, efficient approach to unambiguously characterize Fermi resonances in density functional theory (DFT) based simulations of condensed phase systems. With it, the spectral features can be assigned and the two resonating modes identified. We also show how data from DFT simulations employing classical nuclear dynamics can be post-processed and combined with a perturbative quantum treatment at a finite temperature to include analytically thermal quantum nuclear effects. The inclusion of these effects is crucial to correct some of the qualitative failures of the Newtonian dynamics simulations at a low temperature such as, in particular, the behavior of the frequency splitting of the Fermi dyad. We show, by comparing with experimental data for the paradigmatic case of supercritical CO 2 , that these thermal quantum effects can be substantial even at ambient conditions and that our scheme provides an accurate and computationally convenient approach to account for them.

In this paper, we use probability theory to prove in suitable conditions the equivalence of equilibrium time correlation functions of microscopic density fields with the time correlation functions of local macroscopic density fields evolved by hydrodynamics in (approximate) phenomenological continuum theories of matter. We further discuss a useful and rigorous numerical algorithm, derived from this framework, to compute macroscopic space- and time-dependent behaviors (such as the hydrodynamical one) via molecular dynamics simulations.

We discuss how the Phase Integration Method (PIM), recently developed to compute symmetrized time correlation functions [M. Monteferrante, S. Bonella, and G. Ciccotti, Mol. Phys. 109, 3015 (2011)], can be adapted to sampling/generating the thermal Wigner density, a key ingredient, for example, in many approximate schemes for simulating quantum time dependent properties. PIM combines a path integral representation of the density with a cumulant expansion to represent the Wigner function in a form calculable via existing Monte Carlo algorithms for sampling noisy probability densities. The method is able to capture highly non-classical effects such as correlation among the momenta and coordinates parts of the density, or correlations among the momenta themselves. By using alternatives to cumulants, it can also indicate the presence of negative parts of the Wigner density. Both properties are demonstrated by comparing PIM results to those of reference quantum calculations on a set of model problems.

In spite of its relevant biological role, no general consensus exists on the quantitative characterization of amino acid's hydropathy. In particular, many hydrophobicity scales exist, often producing quite different rankings for the amino acids. To make progress toward a systematic classification, we analyze amino acids' hydropathy based on the orientation of water molecules at a given distance from them as computed from molecular dynamics simulations. In contrast with what is usually done, we argue that assigning a single number is not enough to characterize the properties of an amino acid, in particular when both hydrophobic and hydrophilic regions are present in a residue. Instead we show that appropriately defined conditional probability densities can be used to map the hydrophilic and hydrophobic groups on the amino acids with greater detail than possible with other available methods. Three indicators are then defined based on the features of these probabilities to quantify the specific hydrophobicity and hydrophilicity of each amino acid. The characterization that we propose can be used to understand some of the ambiguities in the ranking of amino acids in the current scales. The quantitative indicators can also be used in combination with standard bioinformatics tools to predict the location of transmembrane regions of proteins. The method is sensitive to the specific environment of the amino acids and can be applied to unnatural and modified amino acids, as well as to other small organic molecules.

The photophysical and photochemical properties of 5-benzyluracil and 5,6-benzyluracil, the latter produced by photocyclization of the former through irradiation with femtosecond UV laser pulses, are investigated both experimentally and theoretically. The absorption spectra of the two molecules are compared, and the principal electronic transitions involved are discussed, with particular emphasis on the perturbation induced on the two chromophore species (uracil and benzene) by their proximity. The photoproduct formation for different irradiation times was verified with high-performance liquid chromatography and nuclear magnetic resonance measurements. The steady-state fluorescence demonstrates that the fluorescence is a distinctive physical observable for detection and selective identification of 5- and 5,6-benzyluracil. The principal electronic decay paths of the two molecules, obtained through TDDFT calculations, explain the features observed in the emission spectra and the photoreactivity of 5-benzyluracil. The order of magnitude of the lifetime of the excited states is derived with steady-state fluorescence anisotropy measurements and rationalized with the help of the computational findings. Finally, the spectroscopic data collected are used to derive the photocyclization and fluorescence quantum yields. In obtaining a global picture of the photophysical and photochemical properties of the two molecules, our findings demonstrates that the use of 5-benzyluracil as a model system to study the proximity relations of a DNA base with a close-lying aromatic amino acid is valid at a local level since the main characteristics of the decay processes from the excited states of the uracil/thymine molecules remain almost unchanged in 5-benzyluracil, the main perturbation arising from the presence of the close-lying aromatic group.

We apply the phase integration method for quasiclassical quantum time correlation functions [M. Monteferrante, S. Bonella, and G. Ciccotti, Mol. Phys. 109, 3015 (2011)] to compute the dynamic structure factor of liquid neon. So far the method had been tested only on model systems. By comparing our results for neon with experiments and previous calculations, we demonstrate that the scheme is accurate and efficient also for a realistic model of a condensed phase system showing quantum behavior.

In this work, the fundamental elements of statistical mechanics underlying the simulation of the protein-ligand binding process, such as statistical ensembles and the concept of microscopic estimators of macroscopic observables and free energy, are summarized in a self consistent fashion. Particular attention is then devoted to the introduction of some mathematical tools that are used in atomistic simulations aimed at estimating binding affinities and free energy profiles, and to the illustration of the origins of the difficulties encountered in this endeavor.

The path integral single sweep method is used to assess quantum effects on the free energy barrier for hydrogen vacancy diffusion in a defective Na(3)AlH(6) crystal. This process has been investigated via experiments and simulations due to its potential relevance in the H release mechanism in sodium alanates, prototypical materials for solid state hydrogen storage. Previous computational studies, which used density functional methods for the electronic structure, were restricted to a classical treatment of the nuclear degrees of freedom. We show that, although they do not change the qualitative picture of the process, nuclear quantum effects reduce the free energy barrier height by about 18% with respect to the classical calculation improving agreement with available neutron scattering data.

We present a study, via experiments and exploratory molecular dynamics simulations, of self aggregation in cylindrical nanostructures obtained experimentally by combining high resolution electron beam lithography with electroless silver deposition. This process is key to the fabrication of a nanolens device, where a strong surface enhancement can be exploited for Raman spectroscopy. In order to investigate the process, we introduce a simple theoretical model and compare the results of simulations with the fabricated silver nanostructures during the growth phase. Our simulations qualitatively agree with the experiments and allow a general characterization of the process at length scales smaller than those easily accessible by microscopy. We identify a geometrical parameter, the aspect ratio of the cylinder, that relates two different types of growth with different characteristics and, possibly, different Raman enhancements., (This journal is © The Royal Society of Chemistry 2012)

Ab initio free energy and rate calculations are performed to investigate two activated mobility processes observed, respectively, in neutron scattering and anelastic spectroscopy experiments on sodium alanates. The system is modeled as a Na(3)AlH(6) crystal hosting one hydrogen vacancy. We identify the process observed via neutron scattering with a positively charged hydrogen vacancy diffusing from the AlH to one of the AlH groups. As for the anelastic spectroscopy experiments, our calculations negate the current hypothesis on the process, i.e. local rearrangement of the H vacancy around the pentacoordinated Al group., (This journal is © the Owner Societies 2011)

Two indicators of the hydropathicity of small solutes are introduced and tested by molecular dynamics simulations. These indicators are defined as probabilities of the orientation of water molecules' dipoles and hydrogen bond vectors, conditional on a generalized distance from the solute suitable for arbitrarily shaped molecules. Using conditional probabilities, it is possible to distinguish features of the distributions in close proximity of the solute. These regions contain the most significant information on the hydration structure but cannot be adequately represented by using, as is usually done, joint distance-angle probability densities. Our calculations show that using our indicators a relative hydropathicity scale for the interesting test set of the quaternary ammonium cations can be roughly determined.

Schofield's form of quantum time correlation functions is used as the starting point to derive a computable expression for these quantities. The time composition property of the propagators in complex time is exploited to approximate Schofield's function in terms of a sequence of short time classical propagations interspersed with path integrals that, combined, represent the thermal density of the system. The approximation amounts to linearization of the real time propagators and it becomes exact with increasing number of propagation legs. Within this scheme, the correlation function is interpreted as an expectation value over a probability density defined on the thermal and real path space and calculated by a Monte Carlo algorithm. The performance of the algorithm is tested on a set of benchmark problems. Although the numerical effort required is considerable, we show that the algorithm converges systematically to the exact answer with increasing number of iterations and that it is stable for times longer than those accessible via a brute force, path integral based, calculation of the correlation function. Scaling of the algorithm with dimensionality is also examined and, when the method is combined with commonly used filtering schemes, found to be comparable to that of alternative semiclassical methods.

The quantum-classical Liouville equation provides a description of the dynamics of a quantum subsystem coupled to a classical environment. Representing this equation in the mapping basis leads to a continuous description of discrete quantum states of the subsystem and may provide an alternate route to the construction of simulation schemes. In the mapping basis the quantum-classical Liouville equation consists of a Poisson bracket contribution and a more complex term. By transforming the evolution equation, term-by-term, back to the subsystem basis, the complex term (excess coupling term) is identified as being due to a fraction of the back reaction of the quantum subsystem on its environment. A simple approximation to quantum-classical Liouville dynamics in the mapping basis is obtained by retaining only the Poisson bracket contribution. This approximate mapping form of the quantum-classical Liouville equation can be simulated easily by Newtonian trajectories. We provide an analysis of the effects of neglecting the presence of the excess coupling term on the expectation values of various types of observables. Calculations are carried out on nonadiabatic population and quantum coherence dynamics for curve crossing models. For these observables, the effects of the excess coupling term enter indirectly in the computation and good estimates are obtained with the simplified propagation.

This paper presents a new approach to propagating the density matrix based on a time stepping procedure arising from a Trotter factorization and combining the forward and backward incremental propagators. The sums over intermediate states of the discrete quantum subsystem are implemented by a Monte Carlo surface hopping-like procedure, while the integrals over the continuous variables are performed using a linearization in the difference between the forward and backward paths of these variables leading to classical-like equations of motion with forces determined by the quantum subsystem states. The approach is tested on several models and numerical convergence is explored.

Linearized mixed quantum-classical simulations are a promising approach for calculating time-correlation functions. At the moment, however, they suffer from some numerical problems that may compromise their efficiency and reliability in applications to realistic condensed-phase systems. In this paper, we present a method that improves upon the convergence properties of the standard algorithm for linearized calculations by implementing a cumulant expansion of the relevant averages. The effectiveness of the new approach is tested by applying it to the challenging computation of the diffusion of an excess electron in a metal-molten salt solution.

Classical trajectory calculations were performed to simulate state-resolved energy transfer experiments of highly vibrationally excited pyrazine (E(vib) = 37,900 cm(-1)) and CO(2), which were conducted using a high-resolution transient infrared absorption spectrometer. The goal here is to use classical trajectories to simulate the supercollision energy transfer pathway wherein large amounts of energy are transferred in single collisions in order to compare with experimental results. In the trajectory calculations, Newton's laws of motion are used for the molecular motion, isolated molecules are treated as collections of harmonic oscillators, and intermolecular potentials are formed by pairwise Lennard-Jones potentials. The calculations qualitatively reproduce the observed energy partitioning in the scattered CO(2) molecules and show that the relative partitioning between bath rotation and translation is dependent on the moment of inertia of the bath molecule. The simulations show that the low-frequency modes of the vibrationally excited pyrazine contribute most to the strong collisions. The majority of collisions lead to small DeltaE values and primarily involve single encounters between the energy donor and acceptor. The large DeltaE exchanges result from both single impulsive encounters and chattering collisions that involve multiple encounters.

We present a new approach for calculating quantum time correlation functions for systems whose dynamics exhibits relevant nonadiabatic effects. The method involves partial linearization of the full quantum path-integral expression for the time correlation function written in the nonadiabatic mapping Hamiltonian formalism. Our analysis gives an algorithm which is both numerically efficient and accurate as we demonstrate in test calculations on the spin-boson model where we find results in good agreement with exact calculations. The accuracy of our new approach is comparable to that of calculations performed using other approximate methods over a relatively broad range of model parameters. However, our method converges relatively quickly when compared with most alternative schemes. These findings are very encouraging in view of the application of the new method for studying realistic nonadiabatic model problems in the condensed phase.

We show that quantum time correlation functions including electronically nonadiabatic effects can be computed by using an approach in which their path integral expression is linearized in the difference between forward and backward nuclear paths while the electronic component of the amplitude, represented in the mapping formulation, can be computed exactly, leading to classical-like equations of motion for all degrees of freedom. The efficiency of this approach is demonstrated in some simple model applications.

We generalize the linearized path integral approach to evaluate quantum time correlation functions for systems best described by a set of nuclear and electronic degrees of freedom, restricting ourselves to the adiabatic approximation. If the operators in the correlation function are nondiagonal in the electronic states, then this adiabatic linearized path integral approximation for the thermal averaged quantum dynamics presents interesting and distinctive features, which we derive and explore in this paper. The capability of these approximations to accurately reproduce the behavior of physical systems is demonstrated by calculating the diffusion constant for an excess electron in a metal-molten salt solution.