Ravishankar Sundararaman

• PhD Physics
• Professor (Assistant) at Rensselaer Polytechnic Institute

Two-dimensional metals generically support gapless plasmons with wavelengths well below the wavelength of free-space radiation at the same frequency. Typically, however, this substantial confinement of electromagnetic energy is associated with commensurately high losses, and mitigating such losses may only be achieved through judicious band structu...

We introduce a computational framework for first-principles density matrix transport within the Wigner function formalism to predict transport of quantum-mechanical degrees of freedom such as spin over long time and length scales. This framework facilitates simulation of spin dynamics and transport from first principles, while accounting for electr...

Machine-learned interatomic potentials (MLPs) have rapidly progressed in accuracy, speed, and data efficiency in recent years. However, training robust MLPs in multicomponent systems still remains a challenge. In this work, we demonstrate a method to physically inform a MLP by $\Delta$-learning the correction to the bonding term in a Dreiding poten...

Intermetallic compounds containing transition metals and group III-V metals tend to possess strong correlations and high catalytic activities, both of which can be enhanced via reduced dimensionality. Nanostructuring is an effective approach to explore this possibility, yet the synthesis of nanostructured intermetallics is challenging due to vast d...

Copper (Cu) interconnects are an increasingly important bottleneck in integrated circuits due to energy consumption and latency caused by the notable increase in Cu resistivity as dimensions decrease, primarily due to electron scattering at surfaces. Herein, the potential of a directional conductor, PtCoO2, which has a low bulk resistivity and a di...

High-throughput density functional theory (DFT) calculations have become a vital element of computational materials science, enabling materials screening, property database generation, and training of “universal” machine learning models. While several software frameworks have emerged to support these computational efforts, new developments such as...

Spin relaxation of electrons in materials involve both reversible dephasing and irreversible decoherence processes. Their interplay leads to a complex dependence of spin relaxation times on the direction and magnitude of magnetic fields, relevant for spintronics and quantum information applications. Here, we use real-time first-principles density m...

Exploring nonequilibrium hot carriers from plasmonic metal nanostructures is a dynamic field in optoelectronics, with applications including photochemical reactions for solar fuel generation. The hot carrier injection mechanism and the reaction rate are highly impacted by the metal/molecule interaction. However, determining the primary type of reac...

The accuracy of density-functional theory (DFT) calculations is ultimately determined by the quality of the underlying approximate functionals, namely the exchange-correlation functional in electronic DFT and the excess functional in the classical DFT formalism of fluids. For both electrons and fluids, the exact functional is highly nonlocal, yet m...

The hybrid organic-inorganic halide perovskite (HOIP), for example MAPbBr3, exhibits extended spin lifetime and apparent spin lifetime anisotropy in experiments. The underlying mechanisms of these phenomena remain illusive. By utilizing our first-principles densitymatrix dynamics approach with quantum scatterings including electron-phonon and elect...

Simulating the dielectric spectra of solvents requires the nuanced definition of inter- and intra-molecular forces. Non-polarizable force fields, while thoroughly benchmarked for dielectric applications, do not capture all the spectral features of solvents, such as water. Conversely, polarizable force fields have been largely untested in the contex...

Electrocatalytic reactions are key to decarbonizing the world economy, but progress in understanding electrocatalytic systems is often hindered by the diversity of conditions under which experiments are run and calculations are performed. This diversity is most often a result of experimental innovation to achieve better electrocatalyst performance,...

Exploring nonequilibrium hot carriers from plasmonic metal nanostructures is a dynamic field in optoelectronics, driving photochemical reactions such as solar fuel generation. The hot carrier injection mechanism and the reaction rate are highly impacted by the metal/molecule interaction. However, determining the primary type of the reaction and thu...

Topological materials confined in 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 template-assisted nanowire...

We present BEAST DB, an open-source database comprised of ab initio electrochemical data computed using grand-canonical density functional theory in implicit solvent at consistent calculation parameters. The database contains over 20,000 surface calculations and covers a broad set of heterogeneous catalyst materials and electrochemical reactions. C...

The accuracy of density-functional theory (DFT) is determined by the quality of the approximate functionals, such as exchange-correlation in electronic DFT and the excess functional in the classical DFT formalism of fluids. The exact functional is highly nonlocal for both electrons and fluids, yet most approximate functionals are semi-local or nonl...

Developing theoretical understanding of complex reactions and processes at interfaces requires using methods that go beyond semilocal density functional theory to accurately describe the interactions between solvent, reactants and substrates. Methods based on many-body perturbation theory, such as the random phase approximation (RPA), have previous...

Modeling complex materials using high-fidelity, ab-initio methods at low cost is a fundamental goal for quantum chemical software packages. The GW approximation and random phase approximation (RPA) provide a unified description of both electronic structure and total energies more accurate than density functional theory (DFT) methods by using the sa...

Protected surface states arising from non-trivial bandstructure topology in semimetals can potentially enable advanced device functionalities in compute, memory, interconnect, sensing, and communication. This necessitates a fundamental understanding of surface-state transport in nanoscale topological semimetals. Here, we investigate quantum transpo...

The atomic‐scale response of inhomogeneous fluids at interfaces and surrounding solute particles plays a critical role in governing chemical, electrochemical, and biological processes. Classical molecular dynamics simulations have been applied extensively to simulate the response of fluids to inhomogeneities directly, but are limited by the accurac...

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 unraveling nanoscale carrier dynam...

Electromagnetic shielding is a critical function in various technologies, which is ideally achieved using a metal that reflects all incident radiation below its plasma frequency. Using high-resolution finite difference frequency domain simulations at microwave/RF frequencies, we show that the same efficacy can be achieved using a disordered collect...

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. Such strong confinement nominally holds the potential to enable optoelectronic technologies that bridge the size difference between photonic and electronic devices...

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...

Spintronics in halide perovskites has drawn significant attention in recent years, due to their highly tunable spin-orbit fields and intriguing interplay with lattice symmetry. Here, we perform first-principles calculations to determine the spin relaxation time (T1) and ensemble spin dephasing time (T2*\documentclass[12pt]{minimal} \usepackage{amsm...

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 dichro...

Precise prediction of phase diagrams in molecular dynamics simulations is challenging due to the simultaneous need for long time and large length scales and accurate interatomic potentials. We show that thermodynamic integration from low-cost force fields to neural network potentials trained using density-functional theory (DFT) enables rapid first...

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 cr...

Harnessing nonequilibrium hot carriers from plasmonic metal nanostructures constitutes a vibrant research field with the potential to control photochemical reactions, particularly for solar fuel generation. However, a comprehensive understanding of the interplay of plasmonic hot-carrier-driven processes in metal/semiconducting heterostructures has...

First-principles calculations for electrochemistry require accurate treatment of both electronic structure and solvation. The perturbative GW approximation starting from density functional theory (DFT) calculations accurately models materials systems with varying dimensionality. Continuum solvation models enable efficient treatment of solvation eff...

Polymer nanodielectrics present a particularly challenging materials design problem for capacitive energy storage applications like polymer film capacitors. High permittivity and breakdown strength are needed to achieve high energy density and loss must be low. Strategies that increase permittivity tend to decrease the breakdown strength and increa...

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/semic...

Luminescence constitutes a unique source of insight into hot carrier processes in metals, including those in plasmonic nanostructures, for sensing and energy applications. However, being weak in nature, metal luminescence remains poorly understood, its microscopic origin strongly debated, and its potential for understanding nanoscale carrier dynami...

Advances in interface science over the last 20 years have demonstrated the use of molecular nanolayers (MNLs) at inorganic interfaces to access emergent phenomena and enhance a variety of interfacial properties. Here, we capture important aspects of how a MNL can induce multifold enhancements and tune multiple interfacial properties, including chem...

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...

We introduce a universal and fully ab initio theory for inelastic scattering of any atom from any surface, and apply the theory to helium scattering from Nb(100). The key aspect making our approach universal is a direct first-principles evaluation of the scattering atom-electron vertex. By correcting misleading results from current state-of-the-art...

The atomic-scale response of inhomogeneous fluids at interfaces and surrounding solute particles plays a critical role in governing chemical, electrochemical and biological processes at such interfaces. Classical molecular dynamics simulations have been applied extensively to simulate the response of inhomogeneous fluids directly, and as inputs to...

First-principles calculations for electrochemistry require accurate treatment of both electronic structure and solvation. The perturbative GW approximation starting from density functional theory (DFT) calculations accurately models materials systems with varying dimensionality. Continuum solvation models enable efficient treatment of solvation eff...

We used machine learning (ML) to accurately predict eigenvalues of the hybrid HSE06 functional using eigenvalues computed by the less computationally expensive PBE and associated electronic features based on the k-point resolved atomic band char- acter. The ML model was trained using eigenvalues from only one k-point for each of the 168 compounds i...

The electrochemical nitrogen reduction reaction (NRR) is a promising route to enable carbon-free ammonia production. However, it is limited by the poor activity and selectivity of current catalysts. The rational design of superior NRR electrocatalysts requires a detailed mechanistic understanding of current material limitations to inform how these...

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,...

We demonstrate a method to compute the dielectric spectra of fluids in molecular dynamics (MD) by directly applying electric fields to the simulation. We obtain spectra from MD simulations with low magnitude electric fields (≈0.01 V/Å) in agreement with spectra from the fluctuation–dissipation method for water and acetonitrile. We examine this meth...

Fully harnessing electrochemical interfaces for reactions requires a detailed understanding of solvent effects in the electrochemical double layer. Predicting the significant impact of solvent on entropic and electronic properties of electrochemical interfaces has remained an open challenge of computational electrochemistry. Using molecular dynamic...

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 dichro...

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...

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...

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, tra...

The resistivity size effect in the ordered intermetallic CuTi compound is quantified using in situ and ex situ thin film resistivity ρ measurements at 295 and 77 K, and density functional theory Fermi surface and electron–phonon scattering calculations. Epitaxial CuTi(001) layers with thickness d = 5.8–149 nm are deposited on MgO(001) at 350 °C and...

Knowing the dielectric properties of the interfacial region in polymer nanocomposites is critical to predicting and controlling dielectric properties. They are, however, difficult to characterize due to their nanoscale dimensions. Electrostatic force microscopy (EFM) provides a pathway to local dielectric property measurements, but extracting local...

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...

Protected surface states arising from non-trivial bandstructure topology in semimetals can potentially enable new device functionalities in compute, memory, interconnect, sensing, and communication. This necessitates a fundamental understanding of surface-state transport in nanoscale topological semimetals. Here, we investigate quantum transport in...

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 h...

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...

Interactions of charge carriers with lattice vibrations, or phonons, play a critical role in unconventional electronic transport of metals and semimetals. Recent observations of phonon-mediated collective electron flow in bulk semimetals, termed electron hydrodynamics, present new opportunities in the search for strong electron-electron interaction...

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...

Polymer Nanodielectrics are class of materials with intriguing combinations of properties. Predicting and designing the properties, however, is complex due to the number of parameters controlling the properties. This makes it difficult to compare results across groups, validate models, and develop a design methodology. This presentation will share...

Spintronic devices, by harnessing the spin degree of freedom, are expected to outperform charge-based devices in terms of energy efficiency and speed of operation. The use of an electric field to control spin at room temperature has been pursued for decades. A major hurdle that has contributed to the slow progress in this regard is the dilemma betw...

Predicting and designing the properties of polymer nanodielectrics is challenging due to the number of parameters controlling properties and the breadth of scale (from electronic to mm). This paper summarizes a preliminary study using elongated semiconducting nanoparticles with an extrinsic interface that enhanced carrier trapping to attempt to fin...

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...

Atomistic simulation of the electrochemical double layer is an ambitious undertaking, requiring quantum mechanical description of electrons, phase space sampling of liquid electrolytes, and equilibration of electrolytes over nanosecond time scales. All models of electrochemistry make different trade-offs in the approximation of electrons and atomic...

We have calculated the time constants of the electron dynamics in traps in a metal-insulator-metal (MIM) plasmonic structure. Because of electron relaxation in metal, the surface plasmon polaritons decays into hot electrons near the surface of the metal, which facilitates the trap of electrons in the interfacial layer of the dielectric. We have cal...

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 enhances spi...

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 ent...

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 are capable of nanosecond to millisecond simulation time are urgently needed. We present a first-princi...

The electrical resistance of interconnect wires increases with decreasing size, causing signal delay and energy consumption that limits further downscaling of integrated circuits. Electron scattering at surfaces and grain-boundaries of current-technology Cu and Co conductors causes the resistivity of narrow lines to be an order of magnitude above b...

This chapter introduces a novel approach to first principles computational electrochemistry that occupies a unique intermediate niche among available approaches, offering the advantages of the alternate approaches without the consequent disadvantages. It presents a new, complementary approach which maintains both computational efficiency and quanti...

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...

Identifying collective variables for chemical reactions is essential to reduce the 3$N$ dimensional energy landscape into lower dimensional basins and barriers of interest. However in condensed phase processes, the non-meaningful motions of bulk solvent often overpower the ability of dimensionality reduction methods to identify correlated motions t...

Identifying collective variables for chemical reactions is essential to reduce the 3$N$ dimensional energy landscape into lower dimensional basins and barriers of interest. However in condensed phase processes, the non-meaningful motions of bulk solvent often overpower the ability of dimensionality reduction methods to identify correlated motions t...

This paper presents a fully ab initio many-body photoemission framework that includes coherent three-body electron-photon-phonon scattering to predict the transverse momentum distributions and the mean transverse energies (MTEs) of bulk photoelectrons from single-crystal photocathodes. The need to develop such a theory stems from the lack of studie...

Metal nanostructures capture light efficiently due to plasmonic enhancement and generate energetic electrons and holes that can be used to drive chemical reactions or transferred across metal–semiconductor interfaces for solar cells and photodetectors. The overall efficiency of plasmonic hot-carrier devices depends on the generated energy distribut...

In situ transport measurements on 5.8–92.1 nm thick epitaxial Ti4SiC3(0001) layers are used to experimentally verify the previously predicted low resistivity scaling. Magnetron co-sputtering from three elemental sources at 1000 °C onto 12-nm-thick TiC(111) nucleation layers on Al2O3(0001) substrates yields epitaxial growth with Ti4SiC3(0001) || Al2...

The detailed understanding of energy transfer between hot electrons and lattice vibrations at non-cryogenic temperatures relies primarily upon the interpretation of ultrafast pump–probe experiments, where thermo-optical models provide insight into the relationship between optical response and temperature of the respective sub-systems; in one of the...

Interphase regions in polymer nanocomposite materials are difficult to characterize due to their nano-scale dimensions. Electrostatic force microscopy (EFM) provides a pathway to local dielectric property measurements, but extracting local dielectric permittivity in complex interphase geometries from EFM measurements remains a challenge. We demonst...

Intermetallic compounds have been proposed as potential interconnect materials for advanced semiconductor devices. This study reports the interdiffusion reliability and resistivity scaling of three low-resistivity intermetallic compounds (Cu2Mg, CuAl2, and NiAl) formed on thermally grown SiO2. Experimental observations and thermodynamic calculation...

Computational quantum chemistry provides fundamental chemical and physical insights into solvated reaction mechanisms across many areas of chemistry, especially in homogeneous and heterogeneous renewable energy catalysis. Such reactions may depend on explicit interactions with ions and solvent molecules that are nontrivial to characterize. Rigorous...

Potential-induced changes in charge and surface structure are significant drivers of the reactivity of electrochemical interfaces but are frequently difficult to decouple from the effects of surface solvation. Here, we consider the Cu(100) surface with a c(2 × 2)-Cl adlayer, a model surface with multiple geometry measurements under both ultrahigh v...

Experimental spin relaxation times in graphene, critical for spintronics and quantum information technologies, are two orders of magnitude below previous theoretical predictions for spin-phonon relaxation. Here, ab initio density-matrix dynamics simulations reveal that electric fields and substrates strongly reduce spin-phonon relaxation time to th...

A fundamental understanding of hot-carrier dynamics in photo-excited metal nanostructures is needed to unlock their potential for photodetection and photocatalysis. Despite numerous studies on the ultrafast dynamics of hot electrons, so far, the temporal evolution of hot holes in metal–semiconductor heterostructures remains unknown. Here, we report...

div>Computational quantum chemistry modeling provides fundamental chemical and physical insights into solvated reaction mechanisms across many areas of chemistry, especially in homogeneous and heterogeneous renewable energy catalysis. Such reactions may depend on explicit interactions with ions and solvent molecules that are non-trivial to characte...

Inspired by the ability of super-resolved fluorescence microscopy to circumvent the diffraction barrier, two-color super-resolution interference lithography exploits non-equilibrium kinetics in materials to achieve large area nanopatterning while using visible light. Periodic patterns with super-resolved features down to tens of nanometers have bee...

Merging concepts from the fields of ab initio materials science and nanophotonics, there is now an opportunity to engineer new photonic materials whose optical, transport, and scattering properties are tailored to attain thermodynamic and quantum limits. Here we present first-principles calculations predicting that Argentene, a single-crystalline h...

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...