arXiv subjects

Zhenbang Dai

Publications and source records attributed to Zhenbang Dai.

17 recordsLinked to original sources

arXiv2026

Nonlinear electron-phonon interactions from first principles

Electron-phonon interactions underpin a variety of phenomena, ranging from transport and superconductivity to polarons and ultrafast carrier dynamics. Despite being one of the most intensely studied subjects in condensed matter physics, research on electron-phonon physics mostly focused on linear, first-order couplings. Second- and higher-order nonlinear couplings are commonly ignored because their calculations are too demanding and we lack computational frameworks that can provide both diagonal and off-diagonal coupling matrix elements. In this work, we report a theory and computational method for computing nonlinear electron-phonon interactions of any order in real materials. Our approach combines the advantages of unit-cell calculations of electron wavefunctions and supercell calculations of phonon perturbations, is systematically improvable, can be used with either semilocal or nonlocal exchange-correlation functionals, and is amenable to Wannier-Fourier interpolation. As a first proof of concept, we illustrate this method by computing second-order electron-phonon coupling matrix elements in diamond, lithium fluoride, and graphite as representative nonpolar semiconductors, polar semiconductors, and metals, respectively. Furthermore, we generalize the ab initio polaron equations to second-order electron-phonon couplings, and we show that second-order couplings are essential to achieve quantitative accuracy in polaron formation energies and hopping barriers. The present methodology will find application in the study of all properties and phenomena that are currently being investigated within the linear electron-phonon coupling approximation, from phonon-mediated superconductivity to excited-states dynamics, both in harmonic and anharmonic systems.

cond-mat.mtrl-sci↗

arXiv2026

Field-unmasked quantum geometry in a symmetry-forbidden photocurrent

Frequency- and polarization-resolved photocurrents provide a sensitive probe of hidden symmetry and band geometry in quantum materials. Here we study a chiral cubic sillenite whose global crystal symmetry forbids a longitudinal odd-in-B magneto-photocurrent in the Voigt geometry. Nevertheless, we observe a pronounced longitudinal response across the visible range that is predominantly linear in magnetic field, persists below the band gap, and exhibits strong helicity selectivity, with the circular channel exceeding the linear one and reversing sign upon switching light helicity. We resolve this apparent contradiction by identifying defect-enabled, field-selected spin ordering as the mechanism that lowers the effective magnetic symmetry without altering the global crystal structure. First-principles calculations show that O vacancies generate in-gap bound states and localized magnetic moments on neighboring Bi-O units, stabilized by strong SOC. Although symmetry-related vacancy configurations remain energetically degenerate and preserve the macroscopic T symmetry at zero field, an applied magnetic field selects a time-reversal-broken sector of the defect ensemble and reduces the effective magnetic symmetry to the subgroup that leaves B invariant, thereby lifting the longitudinal selection rule. Importantly, this field-selected symmetry reduction does more than activate a nominally forbidden photocurrent: it unmasks latent quantum-geometric responses encoded in the electronic structure. Momentum-resolved calculations show that the dominant circular and linear magneto-photocurrent channels spatially correlate with Berry-curvature-rich and quantum-metric-rich regions of the Brillouin zone, respectively. Our results establish field-selected defect symmetry lowering as a route to revealing hidden quantum geometry and activating forbidden nonlinear photocurrents in chiral quantum materials.

cond-mat.mes-hall↗

arXiv2026

Watching Polarons Form in Real Time

Polaron formation in pump-probe experiments is an inherently non-equilibrium phenomenon, driven by the ultrafast coupled dynamics of electrons and phonons, and culminating in the emergence of a localized quasiparticle state. In this work, we present a first-principles quantum-kinetic theory of polaron formation that captures the real-time evolution of electronic and lattice degrees of freedom in presence of electron-phonon coupling. We implement this framework to investigate the ultrafast polaron formation in the prototypical polar insulator MgO. This approach allows us to determine the characteristic timescales of polaron localization and to identify its distinctive dynamical fingerprint. Our results establish clear and experimentally accessible criteria for identifying polaron formation in pump-probe experiments.

cond-mat.mtrl-sci↗

arXiv2025

Polarons from first principles

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.

cond-mat.mtrl-sci↗

arXiv2025

Comparison between first-principles supercell calculations of polarons and the ab initio polaron equations

Polarons are composite quasiparticles formed by excess charges and the accompanying lattice distortions in solids, and play a critical role in transport, optical, and catalytic properties of semiconductors and insulators. The standard approach for calculating polarons from first principles relies on density functional theory and periodic supercells. An alternative approach consists of recasting the calculation of polaron wavefunction, lattice distortion, and energy as a coupled nonlinear eigenvalue problem, using the band structure, phonon dispersions, and the electron-phonon matrix elements as obtained from density functional perturbation theory. Here, we revisit the formal connection between these two approaches, with an emphasis on the handling of self-interaction correction, and we establish a compact formal link between them. We perform a quantitative comparison of these methods for the case of small polarons in the prototypical insulators TiO2, MgO, and LiF. We find that the polaron wavefunctions and lattice distortions obtained from these methods are nearly indistinguishable in all cases, and the formation energies are in good (TiO2) to fair (MgO) agreement. We show that the residual deviations can be ascribed to the neglect of higher-order electron-phonon couplings in the density functional perturbation theory approach.

cond-mat.mtrl-sci↗

arXiv2025

Visualising Policy-Reward Interplay to Inform Zeroth-Order Preference Optimisation of Large Language Models

Fine-tuning Large Language Models (LLMs) with first-order methods like back-propagation is computationally intensive. Zeroth-Order (ZO) optimisation uses function evaluations instead of gradients, reducing memory usage, but suffers from slow convergence in high-dimensional models. As a result, ZO research in LLMs has mostly focused on classification, overlooking more complex generative tasks. In this paper, we introduce ZOPrO, a novel ZO algorithm designed for Preference Optimisation in LLMs. We begin by analysing the interplay between policy and reward models during traditional (first-order) Preference Optimisation, uncovering patterns in their relative updates. Guided by these insights, we adapt Simultaneous Perturbation Stochastic Approximation (SPSA) with a targeted sampling strategy to accelerate convergence. Through experiments on summarisation, machine translation, and conversational assistants, we demonstrate that our method consistently enhances reward signals while achieving convergence times comparable to first-order methods. While it falls short of some state-of-the-art methods, our work is the first to apply Zeroth-Order methods to Preference Optimisation in LLMs, going beyond classification tasks and paving the way for a largely unexplored research direction. Code and visualisations are available at https://github.com/alessioGalatolo/VisZOPrO

cs.CL↗

arXiv2024

Identification of large polarons and exciton polarons in rutile and anatase polymorphs of titanium dioxide

Titanium dioxide (TiO2) is a wide-gap semiconductor with numerous applications in photocatalysis, photovoltaics, and neuromorphic computing. The unique functional properties of this material critically depend on its ability to transport charge in the form of polarons, namely narrow electron wavepackets accompanied by local distortions of the crystal lattice. It is currently well established that the most important polymorphs of TiO2, the rutile and anatase phases, harbor small electron polarons and small hole polarons, respectively. However, whether additional polaronic species exist in TiO2, and under which conditions, remain open questions. Here, we provide definitive answers to these questions by exploring the rich landscape of polaron quasiparticles in TiO2 via recently developed ab initio techniques. In addition to the already known small polarons, we identify three novel species, namely a large hole polaron in rutile, a large quasi-two-dimensional electron polaron in anatase, and a large exciton polaron in anatase. These findings complete the puzzle on the polaorn physics of TiO2 and pave the way for systematically probing and manipulating polarons in a broad class of complex oxides and quantum materials.

cond-mat.mtrl-sci↗

arXiv2024

Ultrafast Vibrational Control of Hybrid Perovskite Devices Reveals the Influence of the Organic Cation on Electronic Dynamics

Vibrational control (VC) of photochemistry through the optical stimulation of structural dynamics is a nascent concept only recently demonstrated for model molecules in solution. Extending VC to state-of-the-art materials may lead to new applications and improved performance for optoelectronic devices. Metal halide perovskites are promising targets for VC due to their mechanical softness and the rich array of vibrational motions of both their inorganic and organic sublattices. Here, we demonstrate the ultrafast VC of FAPbBr3 perovskite solar cells via intramolecular vibrations of the formamidinium cation using spectroscopic techniques based on vibrationally promoted electronic resonance. The observed short (~300 fs) time window of VC highlights the fast dynamics of coupling between the cation and inorganic sublattice. First-principles modelling reveals that this coupling is mediated by hydrogen bonds that modulate both lead halide lattice and electronic states. Cation dynamics modulating this coupling may suppress non-radiative recombination in perovskites, leading to photovoltaics with reduced voltage losses.

physics.app-ph↗

arXiv2024

Theory of excitonic polarons: From models to first-principles calculations

Excitons are neutral excitations that are composed of electrons and holes bound together by their attractive Coulomb interaction. The electron and the hole forming the exciton also interact with the underlying atomic lattice, and this interaction can lead to a trapping potential that favors exciton localization. The quasi-particle thus formed by the exciton and the surrounding lattice distortion is called excitonic polaron. Excitonic polarons have long been thought to exist in a variety of materials, and are often invoked to explain the Stokes shift between the optical absorption edge and the photo-luminescence peak. However, quantitative ab initio calculations of these effects are exceedingly rare. In this manuscript, we present a theory of excitonic polarons that is amenable to first-principles calculations. We first apply this theory to model Hamiltonians for Wannier excitons experiencing Fröhlich or Holstein electron-phonon couplings. We find that, in the case of Fröhlich interactions, excitonic polarons only form when there is a significant difference between electron and hole effective masses. Then, we apply this theory to calculating excitonic polarons in lithium fluoride ab initio. The key advantage of the present approach is that it does not require supercells, therefore it can be used to study a variety of materials hosting either small or large excitonic polarons. This work constitutes the first step toward a complete ab initio many-body theory of excitonic polarons in real materials.

cond-mat.mtrl-sci↗

arXiv2024

Excitonic polarons and self-trapped excitons from first-principles exciton-phonon couplings

Excitons consist of electrons and holes held together by their attractive Coulomb interaction. Although excitons are neutral excitations, spatial fluctuations in their charge density couple with the ions of the crystal lattice. This coupling can lower the exciton energy and lead to the formation of a localized excitonic polaron, or even a self-trapped exciton in the presence of strong exciton-phonon interactions. Here, we develop a theoretical and computational approach to compute excitonic polarons and self-trapped excitons from first principles. Our methodology combines the many-body Bethe-Salpeter approach with density-functional perturbation theory, and does not require explicit supercell calculations. As a proof of concept, we demonstrate our method for a compound of the halide perovskite family.

cond-mat.mtrl-sci↗

arXiv2023

Discovery of enhanced lattice dynamics in a single-layered hybrid perovskite

Layered hybrid perovskites have attracted much attention in recent years due to their emergent physical properties and exceptional functional performances, but the coexistence of lattice order and structural disorder severely hinders our understanding of these materials. One unsolved problem regards how the lattice dynamics are affected by the dimensional engineering of the inorganic frameworks and the interaction with the molecular moieties. Here, we address this question by using a combination of high-resolution spontaneous Raman scattering, high-field terahertz spectroscopy, and molecular dynamics simulations. This approach enables us to reveal the structural vibrations and disorder in and out of equilibrium and provides surprising observables that differentiate single- and double-layered perovskites. While no distinct vibrational coherence is observed in double-layer perovskites, we discover that an off-resonant terahertz pulse can selectively drive a long-lived coherent phonon mode through a two-photon process in the single-layered system. This difference highlights the dramatic change in the lattice environment as the dimension is reduced. The present findings pave the way for the ultrafast structural engineering of hybrid lattices as well as for developing high-speed optical modulators based on layered perovskites.

cond-mat.mtrl-sci↗

arXiv2022

Magnetic Bulk Photovoltaic Effect: Strong and Weak Field

Shift current and ballistic current have been proposed to explain the bulk photovoltaic effect (BPVE), and there have been experiments designed to separate the two mechanisms. These experiments are based on the assumption that under magnetic field, ballistic current can have a Hall effect while the shift current cannot, which is from some energy-scale arguments and has never been proven. A recent work [Phys. Rev. B 103, 195203 (2021)] using quantum transport formalism achieves a conclusion that shift current indeed has a Hall current, seemingly contradicting the previous assumption and making the situation more confusing. Moreover, the behavior of BPVE under strong magnetic field is still unexplored. In this Letter, using a minimal 2D tight-binding model, we carry out a systematic numerical study of the BPVE under weak and strong magnetic field by treating the field in a non-perturbative way. Our model clearly shows the appearance of the magnetically-induced ballistic current along the transverse direction, which agrees with the previous predictions, and interestingly a sizable longitudinal response of the shift current is also observed, a phenomenon that is not captured by any existing theories where the magnetic field is treated perturbatively. More surprisingly, drastically different shift current is found in the strong-field regime, and the evolution from weak to strong field resembles a phase transition. We hope that our work could resolve the debate over the behavior of BPVE under magnetic field, and the strong-field behavior of shift current is expected to inspire more studies on the relation between nonlinear optics and quantum geometry.

cond-mat.mtrl-sci↗

arXiv2022

Recent Progress in the Theory of Bulk Photovoltaic Effect

The bulk photovoltaic effect (BPVE) occurs in solids with broken inversion symmetry and refers to DC current generation due to uniform illumination, without the need of heterostructures or interfaces, a feature that is distinct from the traditional photovoltaic effect. Its existence has been demonstrated almost 50 years ago, but predictive theories only appeared in the last ten years, allowing for the identification of different mechanisms and the determination of their relative importance in real materials. It is now generally accepted that there is an intrinsic mechanism that is insensitive to scattering, called shift current, where first-principles calculations can now give highly accurate predictions. Another important but more extrinsic mechanism, called ballistic current, is also attracting a lot of attention, but due to the complicated scattering processes, its numerical calculation for real materials is only made possible quite recently. In addition, an intrinsic ballistic current, usually referred to as injection current, will appear under circularly-polarized light and has wide application in experiments. In this article, experiments that are pertinent to the theory development are reviewed, and a significant portion is devoted to discussing the recent progress in the theories of BPVE and their numerical implementations. As a demonstration of the capability of the newly developed theories, a brief review of the materials design strategies enabled by the theory development is given. Finally, remaining questions in the BPVE field and possible future directions are discussed to inspire further investigations.

cond-mat.mtrl-sci↗

arXiv2021

First Principles Calculation of Ballistic Current from Electron-Hole Interaction

The bulk photovoltaic effect (BPVE) has attracted an increasing interest due to its potential to overcome the efficiency limit of traditional photovoltaics, and much effort has been devoted to understanding its underlying physics. However, previous work has shown that theoretical models of the shift current and the phonon-assisted ballistic current in real materials do not fully account for the experimental BPVE photocurrent, and so other mechanisms should be investigated in order to obtain a complete picture of BPVE. In this Letter, we demonstrate two approaches that enable the ab initio calculation of the ballistic current originating from the electron-hole interaction in semiconductors. Using BaTiO$_3$ and MoS$_2$ as two examples, we show clearly that for them the asymmetric scattering from electron-hole interaction is less appreciable than that from electron-phonon interaction, indicating more scattering processes need to be included to further improve the BPVE theory. Moreover, our approaches build up a venue for predicting and designing materials with larger ballistic current due to electron-hole interactions.

cond-mat.mtrl-sci↗

arXiv2020

Phonon-Assisted Ballistic Current From First Principles Calculations

The bulk photovoltaic effect (BPVE) refers to current generation due to illumination by light in a homogeneous bulk material lacking inversion symmetry. In addition to the intensively studied shift current, the ballistic current, which originates from asymmetric carrier generation due to scattering processes, also constitutes an important contribution to the overall kinetic model of the BPVE. In this letter, we use a perturbative approach to derive a formula for the ballistic current resulting from the intrinsic electron-phonon scattering in a form amenable to first-principles calculation. We then implement the theory and calculate the ballistic current of the prototypical BPVE material \ch{BaTiO3} using quantum-mechanical density functional theory. The magnitude of the ballistic current is comparable to that of shift current, and the total spectrum (shift plus ballistic) agrees well with the experimentally measured photocurrents. Furthermore, we show that the ballistic current is sensitive to structural change, which could benefit future photovoltaic materials design.

cond-mat.mtrl-sci↗

arXiv2020

The tetragonal phase of CH$_{3}$NH$_{3}$PbI$_{3}$ is strongly anharmonic

Halide perovskite (HP) semiconductors exhibit unique strong coupling between the electronic and structural dynamics. The high-temperature cubic phase of HPs is known to be entropically stabilized, with imaginary frequencies in the calculated phonon dispersion relation. Similar calculations, based on the static average crystal structure, predict a stable tetragonal phase with no imaginary modes. This work shows that in contrast to standard theory predictions, the room-temperature tetragonal phase of CH$_{3} $NH$_{3} $PbI$_{3}$ is strongly anharmonic. We use Raman polarization-orientation (PO) measurements and \textit{ab initio} molecular dynamics (AIMD) to investigate the origin and temperature evolution of the strong structural anharmonicity throughout the tetragonal phase. Raman PO measurements reveal a new spectral feature that resembles a soft mode. This mode shows an unusual continuous increase in damping with temperature which is indicative of an anharmonic potential surface. The analysis of AIMD trajectories identifies two major sources of anharmonicity: the orientational unlocking of the [CH$_{3} $NH$_{3}$]$^+$ ions and large amplitude octahedral tilting that continuously increases with temperature. Our work suggests that the standard phonon picture cannot describe the structural dynamics of tetragonal CH$_{3} $NH$_{3} $PbI$_{3}$.

cond-mat.mtrl-sci↗

arXiv2019

Halide perovskites under polarized light: Vibrational symmetry analysis using polarized Raman

In the last decade, hybrid organic-inorganic halide perovskites have emerged as a new type of semiconductor for photovoltaics and other optoelectronic applications. Unlike standard, tetrahedrally bonded semiconductors (e.g. Si and GaAs), the ionic thermal fluctuations in the halide perovskites (i.e. structural dynamics) are strongly coupled to the electronic dynamics. Therefore, it is crucial to obtain accurate and detailed knowledge about the nature of atomic motions within the crystal. This has proved to be challenging due to low thermal stability and the complex, temperature dependent structural phase sequence of the halide perovskites. Here, these challenges are overcome and a detailed analysis of the mode symmetries is provided in the low-temperature orthorhombic phase of methylammonium-lead iodide. Raman measurements using linearly- and circularly- polarized light at 1.16 eV excitation are combined with density functional perturbation theory (DFPT). By performing an iterative analysis of Raman polarization-orientation dependence and DFPT mode analysis, the crystal orientation is determined. Subsequently, accounting for birefringence effects detected using circularly polarized light excitation, the symmetries of all the observed Raman-active modes at 10 K are assigned.

cond-mat.mtrl-sci↗