Density Matrix Research Articles

Coupling polyatomic molecules to lossy nanocavities: Lindblad vs Schrödinger description.

The use of cavities to impact molecular structure and dynamics has become popular. As cavities, in particular plasmonic nanocavities, are lossy and the lifetime of their modes can be very short, their lossy nature must be incorporated into the calculations. The Lindblad master equation is commonly considered an appropriate tool to describe this lossy nature. This approach requires the dynamics of the density operator and is thus substantially more costly than approaches employing the Schrödinger equation for the quantum wave function when several or many nuclear degrees of freedom are involved. In this work, we compare numerically the Lindblad and Schrödinger descriptions discussed in the literature for a molecular example where the cavity is pumped by a laser. The laser and cavity properties are varied over a range of parameters. It is found that the Schrödinger description adequately describes the dynamics of the polaritons and emission signal as long as the laser intensity is moderate and the pump time is not much longer than the lifetime of the cavity mode. Otherwise, it is demonstrated that the Schrödinger description gradually fails. We also show that the failure of the Schrödinger description can often be remedied by renormalizing the wave function at every step of time propagation. The results are discussed and analyzed.

Efficient Large-Scale Many-Body Quantum Dynamics via Local-Information Time Evolution

During time evolution of many-body systems entanglement grows rapidly, limiting exact simulations to small-scale systems or small timescales. Quantum information tends, however, to flow towards larger scales without returning to local scales, such that its detailed large-scale structure does not directly affect local observables. This allows for the removal of large-scale quantum information in a way that preserves all local observables and gives access to large-scale and large-time quantum dynamics. To this end, we use the recently introduced to organize quantum information into different scales, allowing us to define and that we employ to systematically discard long-range quantum correlations in a controlled way. Our approach relies on decomposing the system into subsystems up to a maximum scale and time evolving the subsystem density matrices by solving the subsystem von Neumann equations in parallel. Importantly, the information flow needs to be preserved during the discarding of large-scale information. To achieve this without the need to make assumptions about the microscopic details of the information current, we introduce a second scale at which information is discarded, while using the state at the maximum scale to accurately obtain the information flow. The resulting algorithm, which we call local-information time evolution, is highly versatile and suitable for investigating many-body quantum dynamics in both closed and open quantum systems with diverse hydrodynamic behaviors. We present results for the energy transport in the mixed-field Ising model and the magnetization transport in the XX spin chain with onsite dephasing where we accurately determine the power-law exponent and the diffusion coefficients. Furthermore, the information lattice framework employed here promises to offer insightful results about the spatial and temporal behavior of entanglement in many-body systems. Published by the American Physical Society 2024

Global quark spin correlations in relativistic heavy ion collisions

The observation of the vector meson’s global spin alignment by the STAR Collaboration reveals that strong spin correlations may exist for quarks and antiquarks in relativistic heavy-ion collisions in the normal direction of the reaction plane. We propose a systematic method to describe such correlations in the quark matter. We classify them as local and long range quark spin correlations in the system. We show in particular that the effective quark spin correlations contain the genuine spin correlations originated directly from the dynamical process as well as those induced by averaging over other degrees of freedom. We also show that such correlations can be studied by measuring the vector meson’s spin density matrix and hyperon-hyperon and hyperon-anti-hyperon spin correlations. We present the relationships between these measurable quantities and spin correlations of quarks and antiquarks. Published by the American Physical Society 2024

Modeling the electroluminescence of atomic wires from quantum dynamics simulations.

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.

The characteristics of heat exchanger for local utilization of wastewater heat under different operating conditions

RELEVANCE. The authors research the local utilization of wastewater heat (in close proximity to the place of their formation) based on a heat exchanger. To select rational characteristics of the heat exchanger and correctly assess the potential energy effect, it is necessary to take into account the influence of the operating conditions of the device (duration of individual use of the shower, mass flow of heated and heating water, temperature of heated water at the inlet to the heat exchanger, temperature of the flow at the moment the device is turned on).THE PURPOSE. The purpose of the work is to research the dependence of the efficiency of wastewater heat utilization on the operating conditions of the heat exchanger and to identify the parameters that have the greatest impact on the effect of energy-saving measures.METHODS. Based on a verified mathematical model of the thermal operation of a recovery heat exchanger, the temperature distribution inside the flows of the heated and heating water in time is calculated (from the moment of switching on until reaching a stationary operating mode). Based on the data obtained (the temperature of the heated water at the outlet of the heat exchanger at each point in time), the absolute and relative heat savings are determined under various operating conditions.RESULTS. The influence of the non-stationary phase of the heat exchanger operation on its energy efficiency is considered. For a specific heat exchanger configuration, the time required for the device to reach a steady state of thermal operation is determined. It was revealed that the greatest influence on the relative and absolute savings of thermal energy is exerted by such operating conditions as mass flow and temperature of heated water at the entrance to the heat exchanger. The temperature of the flow at the initial moment of time has the least influence on the energy effect.CONCLUSION. The operating conditions that have the greatest impact on the effect of local wastewater heat recovery are determined. The need to take these conditions into account when designing a heat exchanger and choosing its optimal parameters has been confirmed.

Poisson geometric formulation of quantum mechanics

We study the Poisson geometrical formulation of quantum mechanics for finite dimensional mixed and pure states. Equivalently, we show that quantum mechanics can be understood in the language of classical mechanics. We review the symplectic structure of the Hilbert space and identify its canonical coordinates. We extend the geometric picture to the space of density matrices DN+. We find it is not symplectic but admits a linear su(N) Poisson structure. We identify Casimir surfaces of DN+ and show that the space of pure states PN≡CPN−1 is one of its symplectic submanifolds which is an intersection of primitive Casimirs. We identify generic symplectic submanifolds of DN+ and calculate their dimensions. We find that DN+ is singularly foliated by the symplectic leaves of varying dimensions, also known as coadjoint orbits. We also find an ascending chain of Poisson submanifolds DNM⊂DNM+1 for 1 ≤ M ≤ N − 1. Each such Poisson submanifold DNM is obtained by tracing out the CM states from the bipartite system CN×CM and is an intersection of N − M primitive Casimirs of DN+. Their Poisson structure is induced from the symplectic structure of the bipartite system. We also show their foliations. Finally, we study the positive semi-definite geometry of the symplectic submanifold ENM consisting of the mixed states with maximum entropy in DNM.

Fundamental role of nonlocal orders in 1D extended Bose-Hubbard model.

Nonlocal order parameters capture the presence of correlated fluctuations between specific degrees of freedom, in otherwise disordered quantum matter. Here, we provide a further example of their fundamental role, deriving the ground state phase diagram of the filling one extended Bose-Hubbard model, exclusively in terms of their ordering. By means of a density matrix renormalization group numerical analysis, we show that in addition to the (even) parity order characteristic of the Mott insulating phase and the string order nonvanishing in the Haldane insulator, the recently proposed odd parity order completes the picture, becoming nonvanishing at the transition from the normal superfluid to the paired superfluid phase. The above three nonlocal parameters capture all the distinct phases, including the density wave phase, in which the local order is seen as the simultaneous presence of correlated fluctuations in different channels. They provide a unique tool for the experimental observation of the full phase diagram of strongly correlated quantum matter, by means of local density measurements.

Predicting the One-Particle Density Matrix with Machine Learning.

Two of the most widely used electronic-structure theory methods, namely, Hartree-Fock and Kohn-Sham density functional theory, require the iterative solution of a set of Schrödinger-like equations. The speed of convergence of such a process depends on the complexity of the system under investigation, the self-consistent-field algorithm employed, and the initial guess for the density matrix. An initial density matrix close to the ground-state matrix will effectively allow one to cut out many of the self-consistent steps necessary to achieve convergence. Here, we predict the density matrix of Kohn-Sham density functional theory by constructing a neural network that uses only the atomic positions as information. Such a neural network provides an initial guess for the density matrix far superior to that of any other recipes available. Furthermore, the quality of such a neural-network density matrix is good enough for the evaluation of interatomic forces. This allows us to run accelerated ab initio molecular dynamics with little to no self-consistent steps.

Krylov complexity of density matrix operators

Quantifying complexity in quantum systems has witnessed a surge of interest in recent years, with Krylov-based measures such as Krylov complexity (CK) and Spread complexity (CS) gaining prominence. In this study, we investigate their interplay by considering the complexity of states represented by density matrix operators. After setting up the problem, we analyze a handful of analytical and numerical examples spanning generic two-dimensional Hilbert spaces, qubit states, quantum harmonic oscillators, and random matrix theories, uncovering insightful relationships. For generic pure states, our analysis reveals two key findings: (I) a correspondence between moment-generating functions (of Lanczos coefficients) and survival amplitudes, and (II) an early-time equivalence between CK and 2CS. Furthermore, for maximally entangled pure states, we find that the moment-generating function of CK becomes the Spectral Form Factor and, at late-times, CK is simply related to NCS for N ≥ 2 within the N-dimensional Hilbert space. Notably, we confirm that CK = 2CS holds across all times when N = 2. Through the lens of random matrix theories, we also discuss deviations between complexities at intermediate times and highlight subtleties in the averaging approach at the level of the survival amplitude.

Chaos in inhomogeneous neutrino fast flavor instability

In dense neutrino gases, the neutrino-neutrino coherent forward scattering gives rise to a complex flavor oscillation phenomenon not fully incorporated in simulations of neutron star mergers (NSM) and core collapse supernovae (CCSNe). Moreover, it has been proposed to be chaotic, potentially limiting our ability to predict neutrino flavor transformations in simulations. To address this issue, we explore how small flavor perturbations evolve in the nonlinear regime of the neutrino quantum kinetic equation within a narrow centimeter-scale region inside a NSM and a toy neutrino distribution. Our findings reveal that paths in the flavor state space of solutions with similar initial conditions diverge exponentially, exhibiting chaos. This inherent chaos makes the microscopic scales of neutrino flavor transformations unpredictable. However, the domain-averaged neutrino density matrix remains relatively stable, with chaos minimally affecting it. This particular property suggests that domain-averaged quantities remain reliable despite the exponential amplification of errors. Published by the American Physical Society 2024

Covariant operator bases for continuous variables

Coherent-state representations are a standard tool to deal with continuous-variable systems, as they allow one to efficiently visualize quantum states in phase space. Here, we work out an alternative basis consisting of monomials on the basic observables, with the crucial property of behaving well under symplectic transformations. This basis is the analogue of the irreducible tensors widely used in the context of SU(2) symmetry. Given the density matrix of a state, the expansion coefficients in that basis constitute the multipoles, which describe the state in a canonically covariant form that is both concise and explicit. We use these quantities to assess properties such as quantumness or Gaussianity and to furnish direct connections between tomographic measurements and quasiprobability distribution reconstructions.

Core Binding Energy Calculations: A Scalable Approach with the Quantum Embedding-Based Equation-of-Motion Coupled-Cluster Method.

We investigated the use of density matrix embedding theory to facilitate the computation of core ionization energies (IPs) of large molecules at the equation-of-motion coupled-cluster singles doubles with perturbative triples (EOM-CCSD*) level in combination with the core-valence separation (CVS) approximation. The unembedded IP-CVS-EOM-CCSD* method with a triple-ζ basis set produced ionization energies within 1 eV of experiment with a standard deviation of ∼0.2 eV for the core65 data set. The embedded variant contributed very little systematic error relative to the unembedded method, with a mean unsigned error of 0.07 eV and a standard deviation of ∼0.1 eV, in exchange for accelerating the calculations by many orders of magnitude. By employing embedded EOM-CC methods, we computed the core ionization energies of the uracil hexamer, doped fullerene, and chlorophyll molecule, utilizing up to ∼4000 basis functions within 1 eV from experimental values. Such calculations are not currently possible with the unembedded EOM-CC method.

Toward Reliable Dipole Moments without Single Excitations: The Role of Orbital Rotations and Dynamical Correlation.

The dipole moment is a crucial molecular property linked to a molecular system's bond polarity and overall electronic structure. To that end, the electronic dipole moment, which results from the electron density of a system, is often used to assess the accuracy and reliability of new electronic structure methods. This work analyses electronic dipole moments computed with the pair coupled cluster doubles (pCCD) ansätze and its linearized coupled cluster (pCCD-LCC) corrections using the canonical Hartree-Fock and pCCD-optimized (localized) orbital bases. The accuracy of pCCD-based dipole moments is assessed against experimental and CCSD(T) reference values using relaxed and unrelaxed density matrices and different basis set sizes. Our test set comprises molecules of various bonding patterns and electronic structures, exposing pCCD-based methods to a wide range of electron correlation effects. Additionally, we investigate the performance of pCCD-in-DFT dipole moments of some model complexes. Finally, our work indicates the importance of orbital relaxation in the pCCD model and shows the limitations of the linearized couple cluster corrections in predicting electronic dipole moments of multiple-bonded systems. Most importantly, pCCD with a linearized CCD correction can reproduce the dipole moment surfaces in singly bonded molecules, which are comparable to the multireference ones.

Chelate Complexes of 3d Transition Metal Ions─A Challenge for Electronic-Structure Methods?

Different electronic-structure methods were assessed for their ability to predict two important properties of the industrially relevant chelating agent nitrilotriacetic acid (NTA): its selectivity with respect to six different first-row transition metal ions and the spin-state energetics of its complex with Fe(III). The investigated methods encompassed density functional theory (DFT), the random phase approximation (RPA), coupled cluster (CC) theory, and the auxiliary-field quantum Monte Carlo (AFQMC) method, as well as the complete active space self-consistent field (CASSCF) method and the respective on-top methods: second-order N-electron valence state perturbation theory (NEVPT2) and multiconfiguration pair-density functional theory (MC-PDFT). Different strategies for selecting active spaces were explored, and the density matrix renormalization group (DMRG) approach was used to solve the largest active spaces. Despite somewhat ambiguous multi-reference diagnostics, most methods gave relatively good agreement with experimental data for the chemical reactions connected to the selectivity, which only involved transition-metal complexes in their high-spin state. CC methods yielded the highest accuracy followed by range-separated DFT and AFQMC. We discussed in detail that even higher accuracies can be obtained with NEVPT2, under the prerequisite that consistent active spaces along the entire chemical reaction can be selected, which was not the case for reactions involving Fe(III). A bigger challenge for electronic-structure methods was the prediction of the spin-state energetics, which additionally involved lower spin states that exhibited larger multi-reference diagnostics. Conceptually different, typically accurate methods ranging from CC theory via DMRG-NEVPT2 in combination with large active spaces to AFQMC agreed well that the high-spin state is energetically significantly favored over the other spin states. This was in contrast to most DFT functionals and RPA which yielded a smaller stabilization and some common DFT functionals and MC-PDFT even predicting the low-spin state to be energetically most favorable.

The Dynamics of the Hubbard Model Through Stochastic Calculus and Girsanov Transformation

As a typical quantum many body problem, we consider the time evolution of density matrix elements in the Bose-Hubbard model. For an arbitrary initial state, these quantities can be obtained from an SDE or stochastic differential equation system. To this SDE system, a Girsanov transformation can be applied. This has the effect that all the information from the initial state moves into the drift part, into the mean field part, of the transformed system. In the large N limit with g=UN\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$g=UN$$\\end{document} fixed, the diffusive part of the transformed system vanishes and as a result, the exact quantum dynamics is given by an ODE system which turns out to be the time dependent discrete Gross Pitaevskii equation. For the two site Bose-Hubbard model, the GP equation reduces to the mathematical pendulum and the difference of expected number of particles at the two lattice sites is equal to the velocity of that pendulum which is either oscillatory or it can have rollovers which then corresponds to the self trapping or insulating phase. As a by-product, we also find an equivalence of the mathematical pendulum with a quartic double well potential. Collapse and revivals are a more subtle phenomenom, in order to see these the diffusive part of the SDE system or quantum corrections have to be taken into account. This can be done with an approximation and collapse and revivals can be reproduced, numerically and also through an analytic calculation. Since expectation values of Fresnel or Wiener diffusion processes, we write the density matrix elements exactly in this way, can be obtained from parabolic second order PDEs, we also obtain various exact PDE representations. The paper has been written with the goal to come up with an efficient calculation scheme for quantum many body systems and as such the formalism is generic and applies to arbitrary dimension, arbitrary hopping matrices and, with suitable adjustments, to fermionic models.

Bexcitonics: Quasiparticle approach to open quantum dynamics.

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.

Theoretical insights into size and dielectric confinement: Unraveling real and imaginary parts of the effective complex dielectric function in spherical multilayered quantum dots with oxide interfaces

A quantitative numerical exploration is conducted to scrutinize the combined effects of size and dielectric confinement consequences on the electronic and optical characteristics of spherical multilayered quantum dot CdSe/ZnS/CdSe/ZnS (SMLQD) and its inverted configuration ZnS/CdSe/ZnS/CdSe (ISMLQD) buried into two oxides: HfO2 and SiO2. By employing the effective mass approximation (EMA) and the density matrix approach (DMA), the derived quantized electron energy states and their associated wave functions were obtained by solving the Schrödinger equation in a spherical coordinates. The dipole transition element, both real and imaginary parts of the effective complex dielectric function (ECDF) as well as its linear, nonlinear and total counterparts are brought out for various values of inner core radii, number density of QDs and incident photon intensity. In addition, a specific analysis of electron probability distributions is provided to gain a clearer understanding of the underlying physical factors. Our findings point to a notable influence of these mentionned factors on the computed coefficients. The study unveils that the dielectric mismatch occurring at the system/oxide interfaces plays a crucial role in modifying the electronic structure and a substantial impact on both linear and third-order nonlinear components is witnessed.

Phase space geometry of general quantum energy transitions

The mixed density operator for coarsegrained eigenlevels of a static Hamiltonian is represented in phase space by the spectral Wigner function, which has its peak on the corresponding classical energy shell. The action of trajectory segments along the shell determine the phase of the Wigner oscillations in its interior. The classical transitions between any pair of energy shells, driven by a general external time dependent Hamiltonian, also have a smooth probability density. It is shown here that a further contribution to the transition between the corresponding pair of coarsegrained energy levels, which oscillates with either energy, or the driving time, is determined by four trajectory segments (two in the pair of energy shells and two generated by the driving Hamiltonian) that join exactly to form a closed compound orbit (CCO). In its turn, this sequence of segments belongs to the semiclassical expression of a compound unitary operator that combines four quantum evolutions: a pair generated by the static internal Hamiltonian and a pair generated by the driving Hamiltonian. The CCOs are shown to belong to continuous families, which are initially seeded at points where the classical flow generated by both Hamiltonians commute.

Effects of temperature and pressure on the limiting current density of PEM electrolysis cells based on a theoretical prediction model and experiments

Operation at high current density of polymer electrolyte membrane electrolysis cell (PEMEC) can reduce its electrode area and capital expense. The high current density operation is limited by the limiting current density (LCD), where electrolysis voltage abruptly increases. Effects of operating temperature and pressure on the LCD were evaluated in a lab-scale PEMEC within a range from 70 to 90 °C and from 0.1 to 0.3 MPa. Also, a theoretical model was developed to predict the LCD, and to clarify what determines LCD and how the operating conditions influence the LCD. The theoretical analysis suggests that when current density is close to the LCD, water mass transport at anode reaches a limitation, which indicates that water saturation reaches almost zero at anodic catalyst layer. The analysis also finds that lower operating temperature and higher operating pressure can reduce oxygen gas saturation and raise the water saturation in porous transport layer at anode, and finally enlarge the LCD.

The Separability Problem in Molecular Quantum Systems: Information-Theoretic Framework for Atoms in Molecules.

Even though molecules are fundamentally quantum entities, the concept of a molecule retains certain classical attributes concerning its constituents. This includes the empirical separability of a molecule into its three-dimensional, rigid structure in Euclidean space, a framework often obtained through experimental methods like X-Ray crystallography. In this work, we delve into the mathematical implications of partitioning a molecule into its constituent parts using the widely recognized Atoms-In-Molecules (AIM) schemes, aiming to establish their validity within the framework of Information Theory concepts. We have uncovered information-theoretical justifications for employing some of the most prevalent AIM schemes in the field of Chemistry, including Hirshfeld (stockholder partitioning), Bader's (topological dissection), and the quantum approach (Hilbert's space definition). In the first approach we have applied the generalized principle of minimum relative entropy derived from the Sharma-Mittal two-parameter functional, avoiding the need for an arbitrary selection of reference promolecular atoms. Within the ambit of topological-information partitioning, we have demonstrated that the Fisher information of Bader's atoms conform to a comprehensive theory based on the Principle of Extreme Physical Information avoiding the need of employing the Schwinger's principle, which has been proven to be problematic. For the quantum approach we have presented information-theoretic justifications for conducting Löwdin symmetric transformations on the density matrix to form atomic Hilbert spaces generating orthonormal atomic orbitals with maximum occupancy for a given wavefunction.