An enormous theoretical effort has been made to treat electron-phonon coupled systems, with particular emphasis on Many Body aspects for dense electron systems, taking into account continuum as well as lattice polaron effects. Treating such aspects of polaron theory has been made possible because of powerful Many Body techniques which include: Exact Diagonalization techniques, Quantum Monte Carlo approaches, Density Matrix renormalization group and Dynamical Mean Field Theory. All these advances in polaron theory needed to be accompanied by: an equally important advance in material research which produced many new materials such as the high Tc cuprates, the manganites and nickelates and the fullerines; as well as significant advances in the refinement of experimental analysis and, in particular, the spectroscopic means such as Angel Resolved Photoemission Spectroscopy, X Ray Absorption Spectroscopy (EXAFS, XANES), Pulsed Neutron Diffraction measurements allowing to study the local dynamical lattice de-formations and optical spectroscopy including time resolved measurements. The scope and purpose of this publication is to review both these theoretical and experimental advances which occurred over the last few decades and to introduce the study of such systems, where both strong electron-electron correlations and large electron-phonon coupling strengths play important roles.
An enormous theoretical effort has been made to treat electron-phonon coupled systems, with particular emphasis on Many Body aspects for dense electron systems, taking into account continuum as well as lattice polaron effects. Treating such aspects of polaron theory has been made possible because of powerful Many Body techniques which include: Exact Diagonalization techniques, Quantum Monte Carlo approaches, Density Matrix renormalization group and Dynamical Mean Field Theory. All these advances in polaron theory needed to be accompanied by: an equally important advance in material research which produced many new materials such as the high Tc cuprates, the manganites and nickelates and the fullerines; as well as significant advances in the refinement of experimental analysis and, in particular, the spectroscopic means such as Angel Resolved Photoemission Spectroscopy, X Ray Absorption Spectroscopy (EXAFS, XANES), Pulsed Neutron Diffraction measurements allowing to study the local dynamical lattice de-formations and optical spectroscopy including time resolved measurements. The scope and purpose of this publication is to review both these theoretical and experimental advances which occurred over the last few decades and to introduce the study of such systems, where both strong electron-electron correlations and large electron-phonon coupling strengths play important roles.
Motivated by aspects of layered high-temperature superconductors and related quasi-one-dimensional materials, we consider polaron structure, dynamics, and coherence in certain extended Peierls–Hubbard models. We emphasize the qualitative importance of electron–lattice interactions even in the presence of dominant electron–electron correlations, the signatures of polaron structure and dynamics in energy-resolved pair-distribution structure functions, and the effect of disorder on polaron propagation and stability. Introduction The formation and dynamics of polarons (and bipolarons), despite a halfcentury of theoretical and experimental study, remain fascinating topics in many-body physics, combining as they do (often competing) aspects of coupled fields with distinct natural time scales (e.g., electron–phonon, spin–phonon, exciton–phonon), electron–electron interactions, lattice discreteness, nonadiabaticity, collective quantum tunneling, thermal fluctuations, competitions between disorder and polaronic localization, etc. Direct observation of polarons through real-space imaging of any of the coupled fields is rare even with the advent of STEM , AFM techniques, etc. Likewise, global measurements such as that of electronic band-structure are insensitive to polaron features. Thus, experiments and theoretical techniques have had to focus on indirect effects on microscopic probes such as transport coefficients, electronic absorption, vibrational spectroscopy, and so forth. Our purpose here is to briefly review three qualitative effects in polaron physics that have arisen in modeling two components of the lattice structure of the layered cuprate superconductors [1] – namely, extended multi-band Peierls–Hubbard models of (a) the active CuO 2 planes and (b) polarizable Cu–O clusters in the axial direction (polarizable interplanar medium).
This article reviews recent theoretical developments in the ab initio study of polarons in materials. The polaron is an emergent quasiparticle that arises from the interaction between electrons and phonons in solids, and consists of an electron or a hole accompanied by a distortion of the crystal lattice. Recent advances in experiments, theory, and computation have made it possible to investigate these quasiparticles with unprecedented detail, reigniting the interest in this classic problem of condensed matter physics. Recent theoretical and computational advances include ab initio calculations of polaron spectral functions, wavefunctions, lattice distortions, and transport and optical properties. These developments provide new insight into polaron physics, but they have evolved somewhat independently from the earlier effective Hamiltonian approaches that laid the foundation of the field. This article aims to bridge these complementary perspectives by placing them within a single unified conceptual framework. To this end, we start by reviewing effective Hamiltonians of historical significance in polaron theory, ab initio techniques based on density functional theory, and many-body first-principles approaches to polarons. After this survey, we outline a general field-theoretic framework that bridges between these diverse approaches to polaron physics. For completeness, we also review recent progress in the study of exciton polarons and self-trapped excitons and their relations to polarons. Beyond the methodology, we discuss recent applications to several classes of materials that attracted attention in the context of polaron physics.
The electron liquid paradigm is at the basis of most of our current understanding of the physical properties of electronic systems. Quite remarkably, the latter are nowadays at the intersection of the most exciting areas of science: materials science, quantum chemistry, nano-electronics, biology, and quantum computation. Accordingly, its importance can hardly be overestimated. During the past 20 years the field has witnessed momentous developments, which are partly covered in this new volume. Advances in semiconductor technology have allowed the realizations of ultra-pure electron liquids whose density, unlike that of the ones spontaneously occurring in nature, can be tuned by electrical means, allowing a systematic exploration of both strongly and weakly correlated regimes. Most of these system are two- or even one-dimensional, and can be coupled together in the form of multi-layers or multi-wires, opening vast observational possibilities. On the theoretical side, quantum Monte Carlo methods have allowed an essentially exact determination of the ground-state energy of the electron liquid, and have provided partial answers to the still open question of the structure of its phase diagram. Starting from the 1980s some truly revolutionary concepts have emerged, which are well represented in this volume.
The crossover from low to high carrier densities in a many-polaron system is studied in the framework of the one-dimensional spinless Holstein model, using unbiased numerical methods. Combining a novel quantum Monte Carlo approach and exact diagonalization, accurate results for the single-particle spectrum and the electronic kinetic energy on fairly large systems are obtained. A detailed investigation of the quality of the Monte Carlo data is presented. In the physically most important adiabatic intermediate electron-phonon coupling regime, for which no analytical results are available, we observe a dissociation of polarons with increasing band filling, leading to normal metallic behavior, while for parameters favoring small polarons, no such density-driven changes occur. The present work points toward the inadequacy of single-polaron theories for a number of polaronic materials such as the manganites.
The discovery of high-Tc superconductivity in cuprates in 1986 moved strongly correlated systems from exotic worlds interesting only for pure theorists to the focus of solid-state research. In recent decades, the majority of hot topics in condensed matter physics (high-Tc superconductivity, colossal magnetoresistance, multiferroicity, ferromagnetism in diluted magnetic semiconductors, etc.) have been related to strongly correlated transition metal compounds. The highly successful electronic structure calculations based on density functional theory lose their predictive power when applied to such compounds. It is necessary to go beyond the mean field approximation and use the many-body theory. The methods and models that were developed for the description of strongly correlated systems are reviewed together with the examples of response function calculations that are needed for the interpretation of experimental information (inelastic neutron scattering, optical conductivity, resonant inelastic X-ray scattering, electron energy loss spectroscopy, angle-resolved photoemission, electron spin resonance, and magnetic and magnetoelectric properties). The peculiarities of (quasi-) 0-, 1-, 2-, and 3- dimensional systems are discussed.
Achieving materials-specific predictions for large, realistic molecules and solids with strong electron correlations remains a long-standing challenge in quantum chemistry. This dissertation develops scalable ab initio quantum many-body methods for crystalline materials, demonstrating that rigorous optimization of theoretical approximations and numerical algorithms enables predictive computation even in strongly correlated systems. The work tackles three interconnected challenges, namely describing material-specific properties of strongly correlated superconductors, achieving linear scaling with k-points for large-scale periodic calculations, and establishing reliable methods for electron-phonon interactions. The following chapters address each challenge in turn. Chapter 2 demonstrates that ab initio density matrix embedding theory, combined with symmetry-breaking strategies for superconducting order parameters, reproduces experimental trends in cuprate superconductivity, including pressure and layer effects on transition temperatures. By directly solving the electronic Schrödinger equation from material structures, these calculations capture multi-orbital covalency effects that simplified model Hamiltonians neglect, revealing their essential role in the spin fluctuations driving pairing. This predictive capability establishes a foundation for efficient computational screening of superconducting materials. Extending these calculations to larger k-point meshes and broader phase diagram explorations, however, demands more efficient computational algorithms. To overcome this computational bottleneck, Chapter 3 introduces interpolative separable density fitting framework. This development enables thermodynamic limit calculations with up to 1000 k-points, as validated on diamond, carbon dioxide, nickel monoxide, and cuprate systems. Integration with density matrix embedding theory and local natural orbital methods further yields converged ground-state energies from accurate correlated wavefunction methods such as CCSD(T) for crystalline materials in the thermodynamic limit. With computational efficiency established, the remaining challenge lies in extending the theoretical framework beyond purely electronic degrees of freedom. Chapter 4 addresses this need by establishing exponential ansatz wavefunctions as competitive approaches for electron-phonon systems. Unlike previous treatments based on perturbation theory, systematic benchmarking of coupled cluster theory and variational Lang-Firsov methods on the Holstein model demonstrates, for the first time, that these approaches accurately describe polaron formation across coupling regimes when combined with appropriate reference state optimization. These results provide a foundation for incorporating phonon effects into ab initio studies of superconducting materials. In addition to these methodological advances, GPU acceleration and MPI parallelization enhance computational throughput, enabling efficient large-scale calculations. Together, these developments constitute a computational framework for predictive ab initio quantum many-body calculations in crystalline materials, opening new avenues for understanding and designing strongly correlated quantum materials.