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Ravishankar Sundararaman

Publications and source records attributed to Ravishankar Sundararaman.

At least 37 records · Page 2Linked to original sources
arXiv2023

Circular Dichroism of Crystals from First Principles

Chiral crystals show promise for spintronic technologies on account of their high spin selectivity, which has led to significant recent interest in quantitative characterization and first-principles prediction of their spin-optoelectronics properties. Here, we outline a computational framework for efficient ab-initio calculations of circular dichroism (CD) in crystalline materials. We leverage direct calculations of orbital angular momentum and quadrupole matrix element calculations in density-functional theory (DFT) and Wannier interpolation to calculate CD in complex materials, removing the need for band convergence and accelerating Brillouin-zone convergence compared to prior approaches. We find strong agreement with measured CD signals in molecules and crystals ranging in complexity from small bulk unit cells to 2D hybrid perovskites, and show the importance of the quadrupole contribution to the anisotropic CD in crystals. Spin-orbit coupling affects the CD of crystals with heavier atoms, as expected, but this is primarily due to changes in the electronic energies, rather than due to direct contributions from the spin matrix elements. We showcase the capability to predict CD for complex structures on a 2D hybrid perovskite, finding strong orientation dependence and identifying the eigen-directions of the unit cell with the strongest CD. We additionally decompose CD into separate contributions from inorganic, organic, and mixed organic-inorganic transitions, finding the chiral molecules to dominate the CD, with the inorganic lattice contributing at higher frequencies in specific directions. This unprecedented level of detail in CD predictions in crystals will facilitate experimental development of complex chiral crystals for spin selectivity.

cond-mat.mtrl-sci↗
arXiv2023

A fully ab initio approach to inelastic atom-surface scattering

We introduce a fully ab initio theory for inelastic scattering of any atom from any surface exciting single phonons, and apply the theory to helium scattering from Nb(100). The key aspect making our approach general is a direct first-principles evaluation of the scattering atom-electron vertex. By correcting misleading results from current state-of-the-art theories, this fully ab initio approach will be critical in guiding and interpreting experiments that adopt next-generation, non-destructive atomic beam scattering.

cond-mat.mtrl-sci↗
arXiv2023

How Spin Relaxes and Dephases in Bulk Halide Perovskites

Spintronics in halide perovskites has drawn significant attention in recent years, due to highly tunable spin-orbit fields and intriguing interplay with lattice symmetry. Spin lifetime -- a key parameter that determines the applicability of materials for spintronics and spin-based quantum information applications -- has been extensively measured in halide perovskites, but not yet assessed from first-principles calculations. Here, we leverage our recently-developed \emph{ab initio} density-matrix dynamics framework to compute the spin relaxation time ($T_{1}$) and ensemble spin dephasing time ($T_{2}^{*}$) in a prototype halide perovskite, namely CsPbBr$_{3}$ with self-consistent spin-orbit coupling (SOC) and quantum descriptions of the electron scattering processes. We also implement the Landé $g$-factor for solids from first principles and take it into account in our dynamics, which is required to accurately capture spin dephasing at external magnetic fields. We thereby predict intrinsic spin lifetimes as an upper bound for experiments, identify the dominant spin relaxation pathways, and evaluate the dependence on temperature, external fields, carrier density,and impurities. Importantly, we find that the Fr{ö}hlich interaction that dominates carrier relaxation contributes negligibly to spin relaxation, consistent with the spin-conserving nature of this interaction. We investigated the effect of spin-orbit field with inversion asymmetry on spin lifetime, and we demonstrated from our calculation, persistent spin helix can enhance spin lifetime when the spin-split is large, but it can not be realized by Rashba SOC. Our theoretical approach may lead to new strategies to optimize spin and carrier transport properties in spintronics and quantum information applications.

cond-mat.mtrl-sci↗
arXiv2023

Quantum-mechanical effects in photoluminescence from thin crystalline gold films

Luminescence constitutes a unique source of insight into hot carrier processes in metals, including those in plasmonic nanostructures used for sensing and energy applications. However, being weak in nature, metal luminescence remains poorly understood, its microscopic origin strongly debated, and its potential for unravelling nanoscale carrier dynamics largely unexploited. Here, we reveal quantum-mechanical effects emanating in the luminescence from thin monocrystalline gold flakes. Specifically, we present experimental evidence, supported by first-principles simulations, to demonstrate its photoluminescence origin when exciting in the interband regime. Our model allows us to identify changes to the measured gold luminescence due to quantum-mechanical effects as the gold film thickness is reduced. Excitingly, such effects are observable in the luminescence signal from flakes up to 40 nm in thickness, associated with the out-of-plane discreteness of the electronic band structure near the Fermi level. We qualitatively reproduce the observations with first-principles modelling, thus establishing a unified description of luminescence in gold and enabling its widespread application as a probe of carrier dynamics and light-matter interactions in this material. Our study paves the way for future explorations of hot-carriers and charge-transfer dynamics in a multitude of material systems.

cond-mat.mtrl-sci↗
arXiv2023

1D-confined crystallization routes for tungsten phosphides

Topological materials confined in one-dimension (1D) can transform computing technologies, such as 1D topological semimetals for nanoscale interconnects and 1D topological superconductors for fault-tolerant quantum computing. As such, understanding crystallization of 1D-confined topological materials is critical. Here, we demonstrate 1D-confined crystallization routes during template-assisted nanowire synthesis where we observe diameter-dependent phase selectivity for topological metal tungsten phosphides. A phase bifurcation occurs to produce tungsten monophosphide and tungsten diphosphide at the cross-over nanowire diameter of ~ 35 nm. Four-dimensional scanning transmission electron microscopy was used to identify the two phases and to map crystallographic orientations of grains at a few nm resolution. The 1D-confined phase selectivity is attributed to the minimization of the total surface energy, which depends on the nanowire diameter and chemical potentials of precursors. Theoretical calculations were carried out to construct the diameter-dependent phase diagram, which agrees with experimental observations. Our find-ings suggest a new crystallization route to stabilize topological materials confined in 1D.

cond-mat.mtrl-sci↗
arXiv2023

Interfacial Hot Carrier Collection Controls Plasmonic Chemistry

Harnessing non-equilibrium hot carriers from plasmonic metal nanostructures constitutes a vibrant research field. It promises to enable control of activity and selectivity of photochemical reactions, especially for solar fuel generation. However, a comprehensive understanding of the interplay of plasmonic hot carrier-driven processes in metal/semiconducting heterostructures has remained elusive. In this work, we reveal the complex interdependence between plasmon excitation, hot carrier generation, transport and interfacial collection in plasmonic photocatalytic devices, uniquely determining the charge injection efficiencies at the solid/solid and solid/liquid interfaces. Interestingly, by measuring the internal quantum efficiency of ultrathin (14 to 33 nm) single-crystalline plasmonic gold (Au) nanoantenna arrays on titanium dioxide substrates, we find that the performance of the device is governed by hot hole collection at the metal/electrolyte interface. In particular, by combining a solid- and liquid-state experimental approach with ab initio simulations, we show a more efficient collection of high-energy d-band holes traveling in [111] orientation, resulting in a stronger oxidation reaction at the {111} surfaces of the nanoantenna. These results thus establish new guidelines for the design and optimization of plasmonic photocatalytic systems and optoelectronic devices.

physics.chem-ph↗
arXiv2023

First-principles molten salt phase diagrams through thermodynamic integration

Precise prediction of phase diagrams in molecular dynamics (MD) simulations is challenging due to the simultaneous need for long time scales, large length scales and accurate interatomic potentials. We show that thermodynamic integration (TI) from low-cost force fields to neural network potentials (NNPs) trained using density-functional theory (DFT) enables rapid first-principles prediction of the solid-liquid phase boundary in the model salt NaCl. We use this technique to compare the accuracy of several DFT exchange-correlation functionals for predicting the NaCl phase boundary, and find that the inclusion of dispersion interactions is critical to obtain good agreement with experiment. Importantly, our approach introduces a method to predict solid-liquid phase boundaries for any material at an ab-initio level of accuracy, with the majority of the computational cost at the level of classical potentials.

cond-mat.mtrl-sci↗
arXiv2023

Highly-confined and tunable plasmonics based on two-dimensional solid-state defect lattices

Plasmons, collective excitations of electrons in solids, are associated with strongly confined electromagnetic fields, with wavelengths far below the wavelength of photons in free space. This strong confinement promises the realization of optoelectronic devices that could bridge the size difference between photonic and electronic devices. However, despite decades of research in plasmonics, many applications remain limited by plasmonic losses, thus motivating a search for new engineered plasmonic materials with lower losses. A promising pathway for low-loss plasmonic materials is the engineering of materials with flat and energetically isolated metallic bands, which can strongly limit phonon-assisted optical losses, a major contributor to short plasmonic lifetimes. Such electronic band structures may be created by judiciously introducing an ordered lattice of defects in an insulating host material. Here, we explore this approach, presenting several low-loss, highly-confined, and tunable plasmonic materials based on arrays of carbon substitutions in hexagonal boron nitride (hBN) monolayers. From our first-principles calculations based on density functional theory (DFT), we find plasmonic structures with mid-infrared plasmons featuring very high confinements ($λ_{\text{vacuum}}/λ_{\text{plasmon}}$ exceeding 2000) and quality factors in excess of 1000. We provide a systematic explanation of how crystal structure, electronic bandwidth, and many-body effects affect the plasmonic dispersions and losses of these materials. The results are thus of relevance to low-loss plasmon engineering in other flat band systems.

physics.optics↗
arXiv2023

Fractional focusing peaks and collective dynamics in two-dimensional Fermi liquids

Carrier transport in materials is often diffusive due to momentum-relaxing scattering with phonons and defects. Suppression of momentum-relaxing scattering can lead to the ballistic and hydrodynamic transport regimes, wherein complex non-Ohmic current flow patterns, including current vortices, can emerge. In the ballistic regime addressed here, transverse magnetic focusing is habitually understood in a familiar single-particle picture of carriers injected from a source, following ballistic cyclotron orbits and reaching a detector. We report on a distinctive nonlocal magnetoresistance phenomenon exclusive to fermions, in an enclosed mesoscopic geometry wherein transverse focusing magnetoresistance peaks also occur at values of the cyclotron diameter that are incommensurate with the distance between the source and detector. In low-temperature experiments and simulations using GaAs/AlGaAs heterostructures with high electron mobility, we show that the peaks occur independently of the location of the detector, and only depend on the source-drain separation. We reproduce the experimental findings using simulations of ballistic transport in both semiclassical and quantum-coherent transport models. The periodicity of magnetic field at which the peaks occur is matched to the lithographically defined device scale. It is found that, unlike in transverse magnetic focusing, the magnetoresistance structure cannot be attributed to any set of ordered single-particle trajectories but instead requires accounting for the collective dynamics of the fermion distribution and of all particle trajectories. The magnetoresistance is further associated with current flow vorticity, a collective phenomenon.

cond-mat.mes-hall↗
arXiv2022

Fermi surface anisotropy in plasmonic metals increases the potential for efficient hot carrier extraction

Realizing the potential of plasmonic hot carrier harvesting for energy conversion and photodetection requires new materials that resolve the bottleneck of extracting carriers prior to energy relaxation within the metal. Using first-principles calculations of optical response and carrier transport properties, we show that directional conductors with Fermi velocities restricted predominantly to one or two directions present significant advantages for efficient hot carrier harvesting. We show that the optical response of film-like conductors, PtCoO$_2$ and Cr$_2$AlC, resemble that of 2D metals, while that of wire-like conductors, CoSn and YCo$_3$B$_2$, resemble that of 1D metals, which can lead to high mode confinement and efficient light collection in small dimensions, while still working with 3D materials with high carrier densities. Carrier lifetimes and transport distances in these materials, especially in PtCoO$_2$ and CoSn, are competitive with noble metals. Most importantly, we predict that carrier injection efficiency from all of these materials into semiconductors can exceed 10% due to the small component of carrier velocity parallel to the metal surface, substantially improving upon the typical less than 0.1% injection efficiency from noble metals into semiconductors.

cond-mat.mtrl-sci↗
arXiv2022

Topological Metal MoP Nanowire for Interconnect

The increasing resistance of Cu interconnects for decreasing dimensions is a major challenge in continued downscaling of integrated circuits beyond the 7-nm technology node as it leads to unacceptable signal delays and power consumption in computing. The resistivity of Cu increases due to electron scattering at surfaces and grain boundaries of the interconnects at the nanoscale. Topological semimetals, owing to their topologically protected surface states and suppressed electron backscattering, are promising material candidates to potentially replace current Cu interconnects as low-resistance interconnects. Here, we report the attractive resistivity scaling of topological metal MoP nanowires and show that the resistivity values are comparable to those of Cu interconnects below 500 nm$^2$ cross-section areas. More importantly, we demonstrate that the dimensional scaling of MoP nanowires, in terms of line resistance versus total cross-sectional area, is superior to those of effective Cu and barrier-less Ru interconnects, suggesting MoP is an attractive solution to the current scaling challenge of Cu interconnects.

cond-mat.mtrl-sci↗
arXiv2022

Ultralow Electron-Surface Scattering in Nanoscale Metals Leveraging Fermi Surface Anisotropy

Increasing resistivity of metal wires with reducing nanoscale dimensions is a major performance bottleneck of semiconductor computing technologies. We show that metals with suitably anisotropic Fermi velocity distributions can strongly suppress electron scattering by surfaces and outperform isotropic conductors such as copper in nanoscale wires. We derive a corresponding descriptor for the resistivity scaling of anisotropic conductors, screen thousands of metals using first-principles calculations of this descriptor and identify the most promising materials for nanoscale interconnects. Previously-proposed layered conductors such as MAX phases and delafossites show promise in thin films, but not in narrow wires due to increased scattering from side walls. We find that certain intermetallics (notably CoSn) and borides (such as YCo$_3$B$_2$) with one-dimensionally anisotropic Fermi velocities are most promising for narrow wires. Combined with first-principles electron-phonon scattering predictions, we show that the proposed materials exhibit 2-3x lower resistivity than copper at 5 nm wire dimensions.

cond-mat.mtrl-sci↗
arXiv2022

Electric fields and substrates dramatically accelerate spin relaxation in graphene

Electrons in graphene are theoretically expected to retain spin states much longer than most materials, making graphene a promising platform for spintronics and quantum information technologies. Here, we use first-principles density-matrix (FPDM) dynamics simulations to show that interaction with electric fields and substrates strongly enhance spin relaxation through scattering with phonons. Consequently, the relaxation time at room temperature reduces from microseconds in free-standing graphene to nanoseconds in graphene on hexagonal boron nitride (hBN) substrate, the order of magnitude typically measured in experiments. Further, inversion symmetry breaking by hBN introduces a stronger asymmetry in electron and hole spin lifetimes, than predicted by the conventional D'yakonov-Perel' (DP) model for spin relaxation. Deviations from the conventional DP model are stronger for in-plane spin relaxation, resulting in out-of-plane to in-plane lifetime ratios much greater than 1/2 with a maximum close to the Dirac point. These FPDM results, independent of symmetry-specific assumptions or material-dependent parameters, also validate recent modifications of the DP model to explain such deviations. Overall, our results indicate that spin-phonon relaxation in the presence of substrates may be more important in graphene than typically assumed, requiring consideration for graphene-based spin technologies at room temperature.

cond-mat.mtrl-sci↗
arXiv2022

Interfacial water asymmetry at ideal electrochemical interfaces

Controlling electrochemical reactivity requires a detailed understanding of the charging behavior and thermodynamics of the electrochemical interface. Experiments can independently probe the overall charge response of the electrochemical double layer by capacitance measurements, and the thermodynamics of the inner layer with potential of maximum entropy (PME) measurements. Relating these properties by computational modeling of the electrochemical interface has so far been challenging due to the low accuracy of classical molecular dynamics (MD) for capacitance and the limited time and length scales of \emph{ab initio} MD (AIMD). Here, we combine large ensembles of long-time-scale classical MD simulations with charge response from electronic density functional theory (DFT) to predict the potential-dependent capacitance of a family of ideal aqueous electrochemical interfaces with different peak capacitances. We show that, while the potential of maximum capacitance varies, this entire family exhibits an electrode charge of maximum capacitance (CMC) between -3.7 $μ$C/cm$^2$ and -3.3 $μ$C/cm$^2$, regardless of details in the electronic response. Simulated heating of the same interfaces reveals that the entropy peaks at a charge of maximum entropy (CME) of $-6.4 \pm 0.7~μ$C/cm$^2$, in agreement with experimental findings for metallic electrodes. The CME and CMC both indicate asymmetric response of interfacial water that is stronger for negatively charged electrodes, while the difference between CME and CMC illustrates the richness in behavior of even the ideal electrochemical interface.

physics.chem-ph↗
arXiv2021

Giant Spin Lifetime Anisotropy and Spin-Valley Locking in Silicene and Germanene from First-Principles Density-Matrix Dynamics

Through First-Principles real-time Density-Matrix (FPDM) dynamics simulations, we investigate spin relaxation due to electron-phonon and electron-impurity scatterings with spin-orbit coupling in two-dimensional Dirac materials - silicene and germanene, at finite temperatures and under external fields. We discussed the applicability of conventional descriptions of spin relaxation mechanisms by Elliott-Yafet (EY) and D'yakonov-Perel' (DP) compared to our FPDM method, which is determined by a complex interplay of intrinsic spin-orbit coupling, external fields, and electron-phonon coupling strength, beyond crystal symmetry. For example, the electric field dependence of spin relaxation time is close to DP mechanism for silicene at room temperature, but rather similar to EY mechanism for germanene. Due to its stronger spin-orbit coupling strength and buckled structure in sharp contrast to graphene, germanene has a giant spin lifetime anisotropy and spin valley locking effect under nonzero Ez and relatively low temperature. More importantly, germanene has extremely long spin lifetime (~100 ns at 50 K) and ultrahigh carrier mobility, which makes it advantageous for spin-valleytronic applications.

cond-mat.mtrl-sci↗
arXiv2021

Ab initio Ultrafast Spin Dynamics in Solids

Spin relaxation and decoherence is at the heart of spintronics and spin-based quantum information science. Currently, theoretical approaches that can accurately predict spin relaxation of general solids including necessary scattering pathways and capable for ns to ms simulation time are urgently needed. We present a first-principles real-time density-matrix approach based on Lindblad dynamics to simulate ultrafast spin dynamics for general solid-state systems. Through the complete first-principles descriptions of pump, probe and scattering processes including electron-phonon, electron-impurity and electron-electron scatterings with self-consistent electronic spin-orbit couplings, our method can directly simulate the ultrafast pump-probe measurements for coupled spin and electron dynamics over ns at any temperatures and doping levels. We first apply this method to a prototypical system GaAs and obtain excellent agreement with experiments. We find that the relative contributions of different scattering mechanisms and phonon modes differ considerably between spin and carrier relaxation processes. In sharp contrast to previous work based on model Hamiltonians, we point out that the electron-electron scattering is negligible at room temperature but becomes dominant at low temperatures for spin relaxation in n-type GaAs. We further examine ultrafast dynamics in novel spin-valleytronic materials - monolayer and bilayer WSe2 with realistic defects. We find that spin relaxation is highly sensitive to local symmetry and chemical bonds around defects. Our work provides a predictive computational platform for spin dynamics in solids, which has unprecedented potentials for designing new materials ideal for spintronics and quantum information technology.

cond-mat.mtrl-sci↗
arXiv2020

Ab initio many-body photoemission theory of transverse energy distribution of photoelectrons: PbTe(111) as a case study with experimental comparisons

This manuscript presents, to our knowledge, the first fully ab initio many-body photoemission framework to predict the transverse momentum distributions and the mean transverse energies (MTEs) of photoelectrons from single-crystal photocathodes. The need to develop such a theory stems from the lack of studies that provide complete understanding of the underlying fundamental processes governing the transverse momentum distribution of photoelectrons emitted from single crystals. For example, initial predictions based on density-functional theory calculations of effective electron masses suggested that the (111) surface of PbTe would produce very small MTEs ($\leq$ 15 meV), whereas our experiments yielded MTEs ten to twenty times larger than these predictions, and also exhibited a lower photoemission threshold than predicted. The ab initio framework presented in this manuscript correctly reproduces the magnitude of the MTEs from our measurements in PbTe(111) and also the observed photoemission below the predicted threshold. Our results show that photoexcitations into bulk-like states and coherent, many-body electron-photon-phonon scattering processes, both of which initial predictions ignored, indeed play important roles in photoemission from PbTe(111). Finally, from the lessons learned, we recommend a procedure for rapid computational screening of potential single-crystal photocathodes for applications in next-generation ultrafast electron diffraction and X-ray free-electron lasers, which will enable new, significant advances in condensed matter research.

cond-mat.mtrl-sci↗
arXiv2020

Spin-phonon relaxation from a universal \emph{ab initio} density-matrix approach

Designing new quantum materials with long-lived electron spin states urgently requires a general theoretical formalism and computational technique to reliably predict intrinsic spin relaxation times. We present a new, accurate and universal first-principles methodology based on Lindbladian dynamics of density matrices to calculate spin-phonon relaxation time ($τ_s$) of solids with arbitrary spin mixing and crystal symmetry. This method describes contributions of Elliott-Yafet (EY) and D'yakonov-Perel' (DP) mechanisms to spin relaxation for systems with and without inversion symmetry on an equal footing. We show that intrinsic spin and momentum relaxation times both decrease with increasing temperature; however, for the DP mechanism, spin relaxation time varies inversely with extrinsic scattering time. We predict large anisotropy of spin lifetime in transition metal dichalcogenides. The excellent agreement with experiments for a broad range of materials underscores the predictive capability of our method for properties critical to quantum information science.

cond-mat.mtrl-sci↗