arXiv subjects

Andrew M. Rappe

Publications and source records attributed to Andrew M. Rappe.

At least 19 recordsLinked to original sources

arXiv2026

Unified First-Principles Theory of Finite-Wave-Vector Photocurrents in Crystals

Spatially structured light carries independent phase and envelope variations in addition to its polarization and frequency. We develop a first-principles theory of second-order dc photocurrents (especially shift and injection) that resolves how these optical degrees of freedom drive distinct dc responses in crystals. The second-order dc response couples two optical field components at the same frequency but with generally different wave vectors. Expanding the response to first order in these wave vectors identifies two rank-four material tensors: $ξ$, which couples to the optical phase gradient and contains the plane-wave photon-drag limit, and $ζ$, which couples to the intensity gradient and describes a spatially varying dc current. Wannier-interpolated calculations for monolayer GeS show symmetry-allowed finite-wave-vector responses that survive at a centrosymmetric structure where conventional bulk photovoltaic effect vanishes. For a Gaussian beam with a uniform phase gradient, the phase-gradient contribution drives current in the same direction on both sides of the beam center, whereas the intensity-gradient contribution drives currents in opposite directions, showing that distinct photocurrent patterns can be selected through the wavefront and envelope of light. A multipolar analysis further resolves the optical corrections into electric-quadrupole, orbital magnetic-dipole, and band-dispersion contributions. Together, these results show how the spatial structure of light can serve as an independent control variable for nonlinear photocurrent generation and provide a first-principles route to predict this response in real materials.

cond-mat.mes-hall↗

arXiv2026

Extrinsic Bulk Photovoltaic Effect from Asymmetric Defect Scattering

The extrinsic bulk photovoltaic effect from asymmetric electron-defect scattering can make an important contribution to the total photocurrent and is highly diagnostic of defect type. We present an ab initio Boltzmann framework combining optical excitation with electron-phonon and symmetric and skew electron-defect scattering, and we apply it to monolayer GeS. Because the defects that generate the current also relax the anisotropy that sustains it, the response peaks at a finite defect fraction. Within the scattering-limited model, cooling to $0$~K shifts the peak position toward lower defect fractions and yields a maximum enhancement of more than six orders of magnitude at fixed defect fraction. At selected low-temperature defect fractions, the total extrinsic current can exceed the intrinsic shift current by more than an order of magnitude, so that the defect fraction itself becomes a tunable parameter.

cond-mat.mtrl-sci↗

arXiv2026

Reading Altermagnetic Domains with Photon Drag

Finite photon momentum allows second-order photocurrents in centrosymmetric space groups, where the conventional bulk photovoltaic effect is forbidden. Here we study the photon-drag response of altermagnets and show that its angular dependence reveals both the symmetry of the magnetic order and the Néel domain of the sample. For example, when a crystal rotation exchanges the two domains, the domain-even and domain-odd parts of the current appear in different angular harmonics, $4n$ and $4n+2$ for tetragonal $d$-wave altermagnets, so that two measurements rotated by $90^\circ$ on a single domain isolate the domain-odd current. We also find that these microscopic contributions exhibit opposite domain parities depending on light polarization. Under linear light, only the shift term is domain odd, while under circular light, the domain-odd channel switches to the injection, Fermi-surface, and contact principal-value terms. Mirror symmetries fix the angular phase of each harmonic and distinguish $d_{x^2-y^2}$, $d_{xy}$, and $g$-wave order. In contrast, conventional collinear antiferromagnets show no domain-odd photon-drag current, and in tetragonal ferromagnets the two parts share the same harmonics. Although the altermagnetic spin splitting does not require spin-orbit coupling (SOC), SOC is essential to observe the domain-odd charge current. Our work uncovers distinct signatures of altermagnetism in photon drag and provides a route to all optical magnetic readouts of altermagnets.

cond-mat.mes-hall↗

arXiv2026

Engineering Grain Boundary Commensurability for Ferroelectric Stabilization in Hafnia-Based Films

Grain boundaries fundamentally dictate the macroscopic properties of polycrystalline materials by breaking long-range symmetry. In ferroelectrics, these structural discontinuities are conventionally considered as detrimental features that induce depolarization fields and accumulate defects, thereby suppressing or pinning local polarization. Here, we demonstrate that the commensurability of grain boundaries inherently governs the polar-orthorhombic phase stability in polycrystalline Hf0.5Zr0.5O2 (HZO) thin films. Using depth-resolved multislice electron ptychography, we map the three-dimensional (3D) phase distribution across diverse boundaries with atomic resolution, revealing that highly commensurate grain boundaries effectively suppress the nonpolar-tetragonal phase by compensating for lattice mismatch while mitigating geometric frustration. Monte Carlo simulations uncover the atomistic and energetic origins of polar-phase stabilization, showing that commensurate grain boundaries favor the polar-orthorhombic phase more strongly than other grain boundaries. Guided by this principle, we epitaxially engineer HZO thin films to promote the preferential formation of commensurate grain boundaries, resulting in an approximately 60% enhancement in the remanent polarization of ferroelectric devices. These findings provide direct 3D experimental and theoretical evidence that establishes grain boundary commensurability as a critical degree of freedom for designing functional interfaces, guiding the construction of novel ceramics and polycrystalline ferroelectrics.

cond-mat.mtrl-sci↗

arXiv2026

Spatially dispersive photogalvanic effects as a probe of quantum geometric tensor

Berry curvature and quantum metric of Bloch states govern a wide range of phenomena, yet unified experimental access to both remains limited. Here we show that light spatial-dispersion alters the selection rules of second-order photocurrents and responses forbidden by parity become allowed in centrosymmetric crystals without any external fields, magnetic order, interfaces, strain, or engineered symmetry breaking. The resulting response is intrinsic and its weight is set by the quantum geometry of the Bloch states. Conventional photogalvanic effects are constrained by crystal symmetry and entangle the quantum metric with shift vector contributions. The spatially-dispersive response instead isolates the quantum metric and Berry curvature in distinct polarization channels. Implementing this approach in 1T'-MoTe2 across its temperature-driven transition to Td-Weyl phase, we resolve helicity-even and helicity-odd photocurrents corresponding to quantum metric and Berry curvature contributions, respectively, from the same device. The metric-dominated response persists across both phases and exhibits a robust spectral structure reproduced by first-principles calculations and linked to momentum-resolved quantum metric hotspots. In contrast, the curvature-driven channel emerges only when inversion symmetry is broken and shows strong sensitivity to carrier doping through competing momentum-space contributions. Our results establish photogalvanic effects with spatially varying optical fields as a general route to accessing quantum geometry in materials where photon energy and electronic filling probe different parts of the excitation manifold.

cond-mat.mes-hall↗

arXiv2026

Defect-Controlled Multiferroicity via Stacking Control in Nonmagnetic van der Waals Bilayers

We present a general paradigm that directly couples vacancy-localized magnetism to interfacial sliding ferroelectricity in nonmagnetic van der Waals (vdWs) bilayers. Utilizing bilayer hexagonal boron nitride (hBN) as a prototypical vdWs host system, we use first-principles calculations to show that a single vacancy acts as a local registry sensor, lifting the degeneracy between polar sliding partners via a defect-centered polarization offset. For interlayer vacancy pairs, we discover a defect selectivity where the hosting sublattice fully dictates the interlayer exchange, stabilizing either ferrimagnetic or antiferromagnetic configurations. Applying an out-of-plane electric field selects the polar registry and drives an amplitude modulation of the compensated Néel order parameter. These findings establish a robust, sublattice-dependent engineering of multiferroic functionality via stacking control across a wide class of nonmagnetic 2D heterostructures.

cond-mat.mtrl-sci↗

arXiv2026

How unconventional oxidation state Au$^{2+}$ is stabilized in halide perovskite Cs$_4$Au$_3$Cl$_{12}$: a first-principles study of its polaron crystal nature

Gold in crystalline compounds is typically only stable in oxidation states Au1+ and Au3+. Even compounds with nominal Au2+ usually disproportionate into Au1+ and Au3+. Recently, Cs4Au3Cl12 was synthesized, where gold took the 2+ state in the bulk. Here, we investigate this compound using first-principles calculations and show that stabilization of the Au2+ ion is through the formation of a polaron crystal. The electronic and phononic structure suggest that the bonding network can be interpreted as a collection of [Au2+Cl4]2- and [Au3+Cl4]1- square planar motifs, and the crystal lacks a smooth pathway for Au2+ to disproportionate into Au1+ and Au3+ without creating dangling bonds. The electronic states of Au are contained within each AuCl4 motif, which allows for the Au2+ state to be localized and isolated electronically. The Au2+-sites form an ordered structure, which is driven by a strong repulsive interaction between [Au2+Cl4]2- motifs due to their lattice distortion. By considering redox reaction, we show that Cs4Au3Cl12 has the maximal density of Au2+, and further reduction will induce a delocalized state. Cs4Au3Cl12 has distinctive electronic structure, with a narrow gap, isolated HOMO and LUMO bands strongly localized at the Au-sites, and magnetization at the Au2+-sites making Cs4Au3Cl12 unique among quantum materials. Cs4Au3Cl12 can be a testbed to explore novel gold chemistry, opening opportunities to control oxidation state through engineering of lattice distortions.

cond-mat.mtrl-sci↗

arXiv2026

Multiphoton Fingerprints of Altermagnetic Spin Splittings

We systematically investigate multiphoton absorption as a polarization-resolved nonlinear optical probe of planar altermagnets (ALMs). We show that the angular harmonic of the altermagnetic spin splitting fixes the lowest optical absorption at which a symmetry-selective response appears: two-photon absorption for $d$-wave order, four-photon absorption for $g$-wave order, and six-photon absorption for $i$-wave order. In each case, there exists a polarization channel locked to the symmetry harmonic of the altermagnetic texture in which the direct $n$-photon contribution to the transition matrix element is absent. This changes the frequency scaling of the absorption rate relative to other polarization channels and provides a direct optical fingerprint of the underlying altermagnetic harmonic. Our results establish a hierarchy of nonlinear spectroscopic signatures that distinguishes $d$-, $g$-, and $i$-wave altermagnetic spin splittings beyond linear response.

cond-mat.mes-hall↗

arXiv2026

Direct spatiotemporal imaging of carriers reveals a long-lived bulk photovoltaic mechanism

The bulk photovoltaic effect (BPVE), a manifestation of broken centrosymmetry, has attracted interest as a probe of the symmetry and quantum geometry of materials, and for use in photovoltaic and optoelectronic devices. However, so far the effect has not been captured directly in space and time. Here, we use contactless pump-probe microscopy to visualize the spatiotemporal evolution of photoexcited carriers in single-crystal, mono-domain $BiFeO_{3}$, a prototypical ferroelectric material. We observe asymmetric carrier transport along the polar axis, which confirms the intrinsic bulk- and symmetry-driven nature of the BPVE. Remarkably, this asymmetric transport persists for several nanoseconds after photoexcitation, which cannot be explained by conventional short-lived shift or phonon ballistic current BPVE mechanisms. Our Monte Carlo simulations show that asymmetric momentum scattering by defects, such as oxygen vacancies, leads to long-lived asymmetric carrier transport, as observed experimentally. Beyond fundamental insights, this paves the way towards controlling symmetry- and defect-driven photoresponses.

cond-mat.mtrl-sci↗

arXiv2026

Mechanochemical Nano-Writing of an Atomically Thin Metal

Mechanical energy accelerates many physicochemical processes, including materials syntheses that are hard to produce with thermal energy alone. However, physical understanding connecting applied mechanical forces with internal stresses and ensuing reaction mechanisms is lacking. Here we demonstrate mechanical force-enabled synthesis and nanoscale patterning to metallize a two-dimensional (2D) material, producing an atomically-thin superconducting material. Localized force applied by atomic force microscope tips to van der Waals (vdW) encapsulated stacks of 2D bilayer MoTe2 and adjacent source Pd guides 2D Pd7MoTe2 growth with 50 nm lateral resolution. Force accelerates reaction kinetics exponentially per Eyring's stress-assisted thermal activation model, reducing synthesis temperatures from ~200 °C to near-room temperature. Finite element simulations, density functional theory, and ab-initio grand canonical Monte Carlo calculations show that tip-induced compression facilitates Pd chemisorption to tensile-strained MoTe2 that converts to uniform Pd7MoTe2. This demonstrates a new, generalizable paradigm for nanoscale synthesis of quantum materials, and high-precision engineering of superconductivity.

cond-mat.mes-hall↗

arXiv2026

Observation of magnetically switchable quantum geometric photocurrents

In non-centrosymmetric materials, light can be rectified into two types of DC photocurrents, known as injection and shift currents, through the bulk photovoltaic effect. Recent theory has uncovered their deep relation with the two-state quantum geometry of resonant transitions: In non-magnetic crystals, where these currents have been routinely observed, the injection current responds to circular light and probes the Berry curvature, while the shift current responds to linear light and probes the geometric connection. Magnetic crystals have been predicted to show a new set of hitherto unobserved magnetically switchable photocurrents, with the roles of linear and circular light interchanged: A linear injection current, which probes the quantum metric, and a circular shift current, which probes the geometric torsion. In this work, we demonstrate the existence of such currents for the first time, demonstrating the switching of the current by flipping the Néel vector in a van der Waals antiferromagnet. Furthermore, their specific frequency and temperature dependence confirm the assignment of circular shift and linear injection currents. Our work demonstrates a new way to control photocurrents in magnets that are directly tied to geometry and have promising applications in antiferromagnetic spintronics and light harvesting.

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↗

arXiv2025

Reconfigurable, non-volatile control of optical anisotropy in ReS2 via ferroelectric gating

Electrically tunable linear dichroism (LD) with non-volatile properties represents a critical yet elusive feature for next-generation integrated photonic elements in practical device architectures. Here, we demonstrate record-breaking, non-volatile control of optical anisotropy in two-dimensional ReS2 via ferroelectric gating with aluminum scandium nitride (AlScN). Our ferroelectric field-effect transistors achieve near-unity (~95%) LD tunability of differential reflectance at room temperature--the highest reported for any electrically controlled 2D optical system. Crucially, the programmed optical states exhibit exceptional retention exceeding 12,000 seconds without applied bias, enabling true non-volatile optical memory. Through combined experimental characterization and ab initio calculations, we reveal that ferroelectric polarization switching induces substantial asymmetric charge transfer to ReS2, selectively populating conduction band states and triggering structural distortions that dramatically enhance optical anisotropy in the "up" polarization state while leaving the "down" state unperturbed. This ferroelectric-semiconductor coupling provides a universal platform for voltage-programmable, energy-efficient photonic devices with dynamic polarization control, addressing critical needs in integrated photonics as well as programmable far-field optics and telecommunications infrastructure.

physics.optics↗

arXiv2024

Ferroelectric Fractals: Switching Mechanism of Wurtzite AlN

The advent of wurtzite ferroelectrics is enabling a new generation of ferroelectric devices for computer memory that has the potential to bypass the von Neumann bottleneck, due to their robust polarization and silicon compatibility. However, the microscopic switching mechanism of wurtzites is still undetermined due to the limitations of density functional theory simulation size and experimental temporal and spatial resolution. Thus, physics-informed materials engineering to reduce coercive field and breakdown in these devices has been limited. Here, the atomistic mechanism of domain wall migration and domain growth in wurtzites is uncovered using molecular dynamics and Monte Carlo simulations of aluminum nitride. We reveal the anomalous switching mechanism of fast 1D single columns of atoms propagating from a slow-moving 2D fractal-like domain wall. We find that the critical nucleus in wurtzites is a single aluminum ion that breaks its bond with one nitrogen and bonds to another nitrogen; this creates a cascade that only flips atoms directly in the same column, due to the extreme locality (sharpness) of the domain walls in wurtzites. We further show how the fractal shape of the domain wall in the 2D plane breaks assumptions in the KAI model and leads to the anomalously fast switching in wurtzite structured ferroelectrics.

cond-mat.mtrl-sci↗

arXiv2024

Domain wall reactions in multiple-order parameter ferroelectrics

The motion of domain walls is crucial for ferroelectric switching. Conventionally, the switching dynamics is believed to be determined by the motion of one or a few low-energy domain wall types of dominant population. Here, we challenge this conventional idea in multiple-order-parameter ferroelectrics. Using hafnia as example, we show that multiple-order-parameter nature not only provides various mobile domain walls and defect-like immobile domain walls, but also enables the domain wall reactions. In analogy with chemical reactions where substances react to form new substances, domain walls could also react to form other domain walls during switching. We identify several elementary domain wall reaction types including synthesis, decomposition, and exchange reactions. Domain walls are continually changed by these reactions during switching so that the switching behavior reflects the statistical average of many domain wall types with distinct mobility and stability. These reactions also lead to phenomenon like remanent nuclei and defect site nucleation that facilitate switching and lower coercive field. Finally, the concept of domain wall reaction is not limited to hafnia but can be generalized to any multiple-order-parameter ferroelectric. This work conceptualizes domain wall reaction, expands theory of ferroelectric switching, and suggests a practical way for defect engineering to control switching behavior.

cond-mat.mtrl-sci↗

arXiv2024

Choosing Tight-Binding Models for Accurate Optoelectronic Responses

Tight-binding models provide great insight and are a low-cost alternative to \emph{ab initio} methods for calculation of a material's electronic structure. These models are used to calculate optical responses, including nonlinear optical effects such as the shift current bulk photovoltaic effect. The validity of tight-binding models is often evaluated by comparing their band structures to those calculated with Density Functional Theory. However, we find that band structure agreement is a necessary but not sufficient condition for accurate optical response calculations. In this Letter, we compute the shift current response and dielectric tensor using a variety of tight-binding models of {MoS$_2$}, including both Slater-Koster and Wannier tight-binding models that treat the Mo $4d$ orbitals and/or S $3p$ orbitals. We also truncate hoppings in the Wannier function models to next-nearest neighbor, as is common in tight-binding methods, in order to gauge the effect on optical response. By examining discrepancies in energies and optical matrix elements, we determine the interpolation quality of the different tight-binding models and establish that agreement in both band structure and wavefunctions is required to accurately model optical response,

cond-mat.mtrl-sci↗

arXiv2024

Bridging experiment and theory of relaxor ferroelectrics at the atomic scale with multislice electron ptychography

Introducing structural and/or chemical heterogeneity into otherwise ordered crystals can dramatically alter material properties. Lead-based relaxor ferroelectrics are a prototypical example, with decades of investigation having connected chemical and structural heterogeneity to their unique properties. While theory has pointed to the formation of an ensemble of ``slush''-like polar domains, the lack of direct, spatially resolved volumetric data comparable to simulations presents a significant challenge in measuring the spatial distribution and correlation of local chemistry and structure with the physics underlying relaxor behavior. Here, we address this challenge through three-dimensional volumetric characterization of the prototypical relaxor ferroelectric \ce{0.68Pb(Mg$_{1/3}$Nb$_{2/3}$)O3-0.32PbTiO$_3$} using multislice electron ptychography. Direct comparison with molecular dynamics simulations reveals the intimate relationship between the polar structure and unit-cell level charge imbalance induced by chemical disorder. Further, polar nanodomains are maintained through local correlations arising from residual short-range chemical order. Acting in concert with the chemical heterogeneities, it is also shown that compressive strain enhances out-of-plane correlations and ferroelectric-like order without affecting the in-plane relaxor-like structure. Broadly, these findings provide a pathway to enable detailed atomic scale understanding for hierarchical control of polar domains in relaxor ferroelectric materials and devices, and also present significant opportunities to tackle other heterogeneous systems using complementary theoretical and experimental studies.

cond-mat.mtrl-sci↗

arXiv2024

Strain fluctuations unlock ferroelectricity in wurtzites

Ferroelectrics are of practical interest for non-volatile data storage due to their reorientable, crystallographically defined polarization. Yet efforts to integrate conventional ferroelectrics into ultrathin memories have been frustrated by film-thickness limitations, which impede polarization reversal under low applied voltage. Wurtzite materials, including magnesium-substituted zinc oxide (Zn,Mg)O, have been shown to exhibit scalable ferroelectricity as thin films. In this work, we explain the origins of ferroelectricity in (Zn,Mg)O, showing that large strain fluctuations emerge locally in (Zn,Mg)O and can reduce local barriers to ferroelectric switching by more than 40%. We provide concurrent experimental and computational evidence of these effects by demonstrating polarization switching in ZnO/(Zn,Mg)O/ZnO heterostructures featuring built-in interfacial strain gradients. These results open up an avenue to develop scalable ferroelectrics by controlling strain fluctuations atomistically.

cond-mat.mtrl-sci↗