Publications

The long-standing problem of predicting the electronic structure of matter on ultra-large scales (beyond 100,000 atoms) is solved with machine learning.

Due to a beneficial balance of computational cost and accuracy, real-time time-dependent density-functional theory has emerged as a promising first-principles framework to describe electron real-time dynamics. Here we discuss recent implementations around this approach, in particular in the context of complex, extended systems. Results include an analysis of the computational cost associated with numerical propagation and when using absorbing boundary conditions. We extensively explore the shortcomings for describing electron-electron scattering in real time and compare to many-body perturbation theory. Modern improvements of the description of exchange and correlation are reviewed. In this work, we specifically focus on the Qb@ll code, which we have mainly used for these types of simulations over the last years, and we conclude by pointing to further progress needed going forward.

The focus of this project is to accelerate and transform the workflow of multiscale materials modeling by developing an integrated toolchain seamlessly combining DFT, SNAP, LAMMPS, (shown in Figure 1-1) and a machine-learning (ML) model that will more efficiently extract information from a smaller set of first-principles calculations. Our ML model enables us to accelerate first-principles data generation by interpolating existing high fidelity data, and extend the simulation scale by extrapolating high fidelity data (10² atoms) to the mesoscale (10⁴ atoms). It encodes the underlying physics of atomic interactions on the microscopic scale by adapting a variety of ML techniques such as deep neural networks (DNNs), and graph neural networks (GNNs). We developed a new surrogate model for density functional theory using deep neural networks. The developed ML surrogate is demonstrated in a workflow to generate accurate band energies, total energies, and density of the 298K and 933K Aluminum systems. Furthermore, the models can be used to predict the quantities of interest for systems with more number of atoms than the training data set. We have demonstrated that the ML model can be used to compute the quantities of interest for systems with 100,000 Al atoms. When compared with 2000 Al system the new surrogate model is as accurate as DFT, but three orders of magnitude faster. We also explored optimal experimental design techniques to choose the training data and novel Graph Neural Networks to train on smaller data sets. These are promising methods that need to be explored in the future.

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We present a numerical modeling workflow based on machine learning which reproduces the total energies produced by Kohn-Sham density functional theory (DFT) at finite electronic temperature to within chemical accuracy at negligible computational cost. Based on deep neural networks, our workflow yields the local density of states (LDOS) for a given atomic configuration. From the LDOS, spatially resolved, energy-resolved, and integrated quantities can be calculated, including the DFT total free energy, which serves as the Born-Oppenheimer potential energy surface for the atoms. We demonstrate the efficacy of this approach for both solid and liquid metals and compare results between independent and unified machine-learning models for solid and liquid aluminum. Our machine-learning density functional theory framework opens up the path towards multiscale materials modeling for matter under ambient and extreme conditions at a computational scale and cost that is unattainable with current algorithms.

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Through a combination of single crystal growth, experiments involving in situ deposition of surface adatoms, and complimentary modeling, we examine the electronic transport properties of lithium-decorated ZrTe5 thin films. We observe that the surface states in ZrTe5 are robust against Li adsorption. Both the surface electron density and the associated Berry phase are remarkably robust to adsorption of Li atoms. Fitting to the Hall conductivity data reveals that there exist two types of bulk carriers: those for which the carrier density is insensitive to Li adsorption, and those whose density decreases during initial Li depositions and then saturates with further Li adsorption. We propose this dependence is due to the gating effect of a Li-adsorption-generated dipole layer at the ZrTe5 surface.

The self-interstitial atom (SIA) is one of two fundamental point defects in bulk Si. Isolated Si SIAs are extremely difficult to observe experimentally. Even at very low temperatures, they anneal before typical experiments can be performed. Given the challenges associated with experimental characterization, accurate theoretical calculations provide valuable information necessary to elucidate the properties of these defects. Previous studies have applied Kohn-Sham density functional theory (DFT) to the Si SIA, using either the local density approximation or the generalized gradient approximation to the exchange-correlation (XC) energy. The consensus of these studies indicates that a Si SIA may exist in five charge states ranging from -2 to +2 with the defect structure being dependent on the charge state. This study aims to re-examine the existence of these charge states in light of recently derived "approximate bounds"on the defect levels obtained from finite-size supercell calculations and new DFT calculations using both semi-local and hybrid XC approximations. We conclude that only the neutral and +2 charge states are directly supported by DFT as localized charge states of the Si SIA. Within the current accuracy of DFT, our results indicate that the +1 charge state likely consists of an electron in a conduction-band-like state that is coulombically bound to a +2 SIA. Furthermore, the -1 and -2 charge states likely consist of a neutral SIA with one and two additional electrons in the conduction band, respectively.

Recent years have seen an explosion in research efforts discovering and understanding novel electronic and optical properties of topological quantum materials (TQMs). In this LDRD, a synergistic effort of materials growth, characterization, electrical-magneto-optical measurements, combined with density functional theory and modeling has been established to address the unique properties of TQMs. Particularly, we have carried out extensive studies in search for Majorana fermions (MFs) in TQMs for topological quantum computation. Moreover, we have focused on three important science questions. 1) How can we controllably tune the properties of TQMs to make them suitable for quantum information applications? 2) What materials parameters are most important for successfully observing MFs in TQMs? 3) Can the physical properties of TQMs be tailored by topological band engineering? Results obtained in this LDRD not only deepen our current knowledge in fundamental quantum physics but also hold great promise for advanced electronic/photonic applications in information technologies. ACKNOWLEDGEMENTS The work at Sandia National Labs was supported by a Laboratory Directed Research and Development project. Device fabrication was performed at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. We are grateful to many people inside and outside Sandia for their support and fruitful collaborations. This report describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.

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Detailed understanding of solid–solid interface structure–function relationships is critical for the improvement and wide deployment of all-solid-state batteries. The interfaces between lithium phosphorous oxynitride (LiPON) solid electrolyte material and lithium metal anode, and between LiPON and LixCoO2 cathode, have been reported to generate solid–electrolyte interphase (SEI)-like products and/or disordered regions. Using electronic structure calculations and crystalline LiPON models, we predict that LiPON models with purely P−N−P backbones are kinetically inert towards lithium at room temperature. In contrast, transfer of oxygen atoms from low-energy LixCoO2(104) surfaces to LiPON is much faster under ambient conditions. The mechanisms of the primary reaction steps, LiPON structural motifs that readily reacts with lithium metal, experimental results on amorphous LiPON to partially corroborate these predictions, and possible mitigation strategies to reduce degradations are discussed. LiPON interfaces are found to be useful case studies for highlighting the importance of kinetics-controlled processes during battery assembly at moderate processing temperatures.

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The formulation of carrier transport through heterojunctions by tunneling and thermionic emission is derived from first principles. The treatment of tunneling is discussed at three levels of approximation: numerical solution of the one-band envelope equation for an arbitrarily specified potential profile; the WKB approximation for an arbitrary potential; and, an analytic formulation assuming constant internal field. The effects of spatially varying carrier chemical potentials over tunneling distances are included. Illustrative computational results are presented. The described approach is used in exploratory physics models of irradiated heterojunction bipolar transistors within Sandia's QASPR program.

The energy-dependent probability density of tunneled carrier states for arbitrarily specified longitudinal potential-energy profiles in planar bipolar devices is numerically computed using the scattering method. Results agree accurately with a previous treatment based on solution of the localized eigenvalue problem, where computation times are much greater. These developments enable quantitative treatment of tunneling-assisted recombination in irradiated heterojunction bipolar transistors, where band offsets may enhance the tunneling effect by orders of magnitude. The calculations also reveal the density of non-tunneled carrier states in spatially varying potentials, and thereby test the common approximation of uniform- bulk values for such densities.

We show scaling results for materials of interest in Sandia Radiation-Effects and High-Energy-Density-Physics Mission Areas. Each timing is from a self-consistent calculation for bulk material. Two timings are given: (1) walltime for the construction of the CR exchange operator (Exchange-Operator) and (2) walltime for everything else (non-Exchange-Operator).

Predicting transient effects caused by short - pulse neutron irradiation of electronic devices is an important part of Sandia's mission. For example , predicting the diffusion of radiation - induced point defects is needed with in Sandia's Qualification Alternative to the Sandia Pulsed Reactor (QASPR) pro gram since defect diffusion mediates transient gain recovery in QASPR electronic devices. Recently, the semiconductors used to fabricate radiation - hard electronic devices have begun to shift from silicon to III - V compounds such as GaAs, InAs , GaP and InP . An advantage of this shift is that it allows engineers to optimize the radiation hardness of electronic devices by using alloy s such as InGaAs and InGaP . However, the computer codes currently being used to simulate transient radiation effects in QASP R devices will need to be modified since they presume that defect properties (charge states, energy levels, and diffusivities) in these alloys do not change with time. This is not realistic since the energy and properties of a defect depend on the types of atoms near it and , therefore, on its location in the alloy. In particular, radiation - induced defects are created at nearly random locations in an alloy and the distribution of their local environments - and thus their energies and properties - evolves with time as the defects diffuse through the alloy . To incorporate these consequential effects into computer codes used to simulate transient radiation effects, we have developed procedures to accurately compute the time dependence of defect energies and properties and then formulate them within compact models that can be employed in these computer codes. In this document, we demonstrate these procedures for the case of the highly mobile P interstitial (I P ) in an InGaP alloy. Further dissemination only as authorized to U.S. Government agencies and their contractors; other requests shall be approved by the originating facility or higher DOE programmatic authority.

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The application of first-principles calculations holds promise for greatly improving our understanding of semiconductor superlattices. Developing a procedure to accurately predict band gaps using hybrid density functional theory lays the groundwork for future studies investigating more nuanced properties of these structures. Our approach allows a priori prediction of the properties of SLS structures using only the band gaps of the constituent materials. Furthermore, it should enable direct investigation of the effects of interface structure, e.g., intermixing or ordering at the interface, on SLS properties. In this paper, we present band gap data for various InAs/GaSb type-II superlattice structures calculated using the generalized Kohn-Sham formulation of density functional theory. A PBE0-type hybrid functional was used, and the portion of the exact exchange was tuned to fit the band gaps of the binary compounds InAs and GaSb with the best agreement to bulk experimental values obtained with 18% of the exact exchange. The heterostructures considered in this study are 6 monolayer (ML) InAs/6 ML GaSb, 8 ML InAs/8 ML GaSb and 10 ML InAs/10 ML GaSb with deviations from the experimental band gaps ranging from 3% to 11%.

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Carrier transport and recombination are modeled for a heterojunction diode containing irradiation defects. Detailed attention is given to the role of band-to-trap tunneling and how it is affected by band offsets at the junction. Tunneled states are characterized by numerical solution of the one-band effective-mass envelope equation. The interaction with traps is treated assuming capture by the multi-phonon-emission mechanism. It is shown that tunneling can increase carrier recombination at defects by orders of magnitude in the presence of large band offsets. This explains why Npn InGaP/GaAs/GaAs heterojunction bipolar transistors with displacement damage from energetic-particle irradiation are observed to have high carrier recombination in the emitter-base depletion region.

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This report examines the temperature dependence of the capture rate of carriers by defects in gallium arsenide and compares two previously published theoretical treatments of this based on multi phonon emission (MPE). The objective is to reduce uncertainty in atomistic simulations of gain degradation in III-V HBTs from neutron irradiation. A major source of uncertainty in those simulations is poor knowledge of carrier capture rates, whose values can differ by several orders of magnitude between various defect types. Most of this variation is due to different dependence on temperature, which is closely related to the relaxation of the defect structure that occurs as a result of the change in charge state of the defect. The uncertainty in capture rate can therefore be greatly reduced by better knowledge of the defect relaxation.

We performed density functional theory (DFT) calculations for a bi-layered heterostructure combining a graphene layer with a MoS₂ layer with and without intercalated Li atoms. Our calculations demonstrate the importance of the van der Waals (vdW) interaction, which is crucial for forming stable bonding between the layers. Our DFT calculation correctly reproduces the linear dispersion, or Dirac cone, feature at the Fermi energy for the isolated graphene monolayer and the band gap for the MoS₂ monolayer. For the combined graphene/MoS₂ bi-layer, we observe interesting electronic structure and density of states (DOS) characteristics near the Fermi energy, showing both the gap like features of the MoS₂ layer and in-gap states with linear dispersion contributed mostly by the graphene layer. Our calculated total DOS in this vdW heterostructure reveals that the graphene layer significantly contributes to pinning the Fermi energy at the center of the band gap of MoS₂. We also find that intercalating Li ions in between the layers of the graphene/MoS2 heterostructure enhances the binding energy through orbital hybridizations between cations (Li adatoms) and anions (graphene and MoS₂ monolayers). Moreover, we calculate the dielectric function of the Li intercalated graphene/MoS₂ heterostructure, the imaginary component of which can be directly compared with experimental measurements of optical conductivity in order to validate our theoretical prediction. We observe sharp features in the imaginary component of the dielectric function, which shows the presence of a Drude peak in the optical conductivity, and therefore metallicity in the lithiated graphene/MoS₂ heterostructure.

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Classical molecular dynamics (MD) provides a powerful and widely used approach to determining thermodynamic properties by integrating the classical equations of motion of a system of atoms. Time-Dependent Density Functional Theory (TDDFT) provides a powerful and increasingly useful approach to integrating the quantum equations of motion for a system of electrons. TDDFT efficiently captures the unitary evolution of a many-electron state by mapping the system into a fictitious non-interacting system. In analogy to MD, one could imagine obtaining the thermodynamic properties of an electronic system from a TDDFT simulation in which the electrons are excited from their ground state by a time-dependent potential and then allowed to evolve freely in time while statistical data are captured from periodic snapshots of the system. For a variety of systems (e.g., many metals), the electrons reach an effective state of internal equilibrium due to electron-electron interactions on a time scale that is short compared to electron-phonon equilibration. During the initial time-evolution of such systems following electronic excitation, electron-phonon interactions should be negligible, and therefore, TDDFT should successfully capture the internal thermalization of the electrons. However, it is unclear how TDDFT represents the resulting thermal state. In particular, the thermal state is usually represented in quantum statistical mechanics as a mixed state, while the occupations of the TDDFT wavefunctions are fixed by the initial state in TDDFT. We work to address this puzzle by (A) reformulating quantum statistical mechanics so that thermodynamic expectations can be obtained as an unweighted average over a set of many-body pure states and (B) constructing a family of non-interacting (single determinant) TDDFT states that approximate the required many-body states for the canonical ensemble.

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A recently developed bounds-analysis approach has been used to interpret density-functional-theory (DFT) results for the As and Ga antisites in GaAs. The bounds analysis and subsequent processing of DFT results for the As antisite yielded levels - defined as the Fermi levels at which the defect charge state changes - in very good agreement with measurements, including the -1/0 level which is within 0.1 eV of the conduction-band edge. Good agreement was also obtained for the activation energies to transform the AsGa from its metastable state to its stable state. For the Ga antisite, the bounds analysis revealed that the -1 and 0 charge states are hole states weakly bound to a localized -2 charge state. The calculated levels are in good agreement with measurements.

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Carrier recombination due to defects can have a major impact on device performance. The rate of defect-induced carrier recombination is determined by both defect levels and carrier capture cross-sections. Kohn-Sham density functional theory (DFT) has been widely and successfully used to predict defect levels in semiconductors and insulators, but only recently has work begun to focus on using DFT to determine carrier capture cross-sections. Lang and Henry worked out the fundamental theory of carrier-capture cross-sections in the 1970s and showed that, in most cases, room temperature carrier-capture cross-sections differ between defects primarily due to differences in the carrier capture activation energies. Here, we present an approach to using DFT to calculate carrier capture activation energies that does not depend on perturbation theory or an assumed configuration coordinate, and we demonstrate this approach for the -3/-2 level of the Ga vacancy in wurtzite GaN.

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In modeling thermal transport in nanoscale systems, classical molecular dynamics (MD) explicitly represents phonon modes and scattering mechanisms, but electrons and their role in energy transport are missing. Furthermore, the assumption of local equilibrium between ions and electrons often fails at the nanoscale. We have coupled MD (implemented in the LAMMPS MD package) with a partial differential equation based representation of the electrons (implemented using finite elements). The coupling between the subsystems occurs via a local version of the two-temperature model. Key parameters of the model are calculated using the Time Dependent Density Functional Theory with either explicit or implicit energy flow. We will discuss application of this work in the context of the US DOE Center for Integrated Nanotechnologies (CINT).

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Understanding internal dissipation in resonant mechanical systems at the micro- and nanoscale is of great technological and fundamental interest. Resonant mechanical systems are central to many sensor technologies, and microscale resonators form the basis of a variety of scanning probe microscopies. Furthermore, coupled resonant mechanical systems are of great utility for the study of complex dynamics in systems ranging from biology to electronics to photonics. In this work, we report the detailed experimental study of internal dissipation in micro- and nanomechanical oscillators fabricated from amorphous and crystalline diamond materials, atomistic modeling of dissipation in amorphous, defect-free, and defect-containing crystalline silicon, and experimental work on the properties of one-dimensional and two-dimensional coupled mechanical oscillator arrays. We have identified that internal dissipation in most micro- and nanoscale oscillators is limited by defect relaxation processes, with large differences in the nature of the defects as the local order of the material ranges from amorphous to crystalline. Atomistic simulations also showed a dominant role of defect relaxation processes in controlling internal dissipation. Our studies of one-dimensional and two-dimensional coupled oscillator arrays revealed that it is possible to create mechanical systems that should be ideal for the study of non-linear dynamics and localization.

A finite temperature version of 'exact-exchange' density functional theory (EXX) has been implemented in Sandia's Socorro code. The method uses the optimized effective potential (OEP) formalism and an efficient gradient-based iterative minimization of the energy. The derivation of the gradient is based on the density matrix, simplifying the extension to finite temperatures. A stand-alone all-electron exact-exchange capability has been developed for testing exact exchange and compatible correlation functionals on small systems. Calculations of eigenvalues for the helium atom, beryllium atom, and the hydrogen molecule are reported, showing excellent agreement with highly converged quantumMonte Carlo calculations. Several approaches to the generation of pseudopotentials for use in EXX calculations have been examined and are discussed. The difficult problem of finding a correlation functional compatible with EXX has been studied and some initial findings are reported.

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The optimized effective potential (OEP) method provides an additional level of exactness in the computation of electronic structures, e.g. the exact exchange energy can be used. This extra freedom is likely to be important in moving density functional methods beyond traditional approximations such as the local density approximation. We provide a new density-matrix-based derivation of the gradient of the Kohn-Sham energy with respect to the effective potential. This gradient can be used to iteratively minimize the energy in order to find the OEP. Previous work has indicated how this can be done in the zero temperature limit. This paper generalizes the previous results to the finite temperature regime. Equating our gradient to zero gives a finite temperature version of the OEP equation. © IOP Publishing Ltd.

We report the implementation of an iterative scheme for calculating the Optimized Effective Potential (OEP). Given an energy functional that depends explicitly on the Kohn-Sham wave functions, and therefore, implicitly on the local effective potential appearing in the Kohn-Sham equations, a gradient-based minimization is used to find the potential that minimizes the energy. Previous work has shown how to find the gradient of such an energy with respect to the effective potential in the zero-temperature limit. We discuss a density-matrix-based derivation of the gradient that generalizes the previous results to the finite temperature regime, and we describe important optimizations used in our implementation. We have applied our OEP approach to the Hartree-Fock energy expression to perform Exact Exchange (EXX) calculations. We report our EXX results for common semiconductors and ordered phases of hydrogen at zero and finite electronic temperatures. We also discuss issues involved in the implementation of forces within the OEP/EXX approach.

The potential for implementing quantum coherence in semiconductor self-assembled quantum dots has been investigated theoretically and experimentally. Theoretical modeling suggests that coherent dynamics should be possible in self-assembled quantum dots. Our experimental efforts have optimized InGaAs and InAs self-assembled quantum dots on GaAs for demonstrating coherent phenomena. Optical investigations have indicated the appropriate geometries for observing quantum coherence and the type of experiments for observing quantum coherence have been outlined. The optical investigation targeted electromagnetically induced transparency (EIT) in order to demonstrate an all optical delay line.

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The goal of this LDRD was to investigate III-antimonide/nitride based materials for unique semiconductor properties and applications. Previous to this study, lack of basic information concerning these alloys restricted their use in semiconductor devices. Long wavelength emission on GaAs substrates is of critical importance to telecommunication applications for cost reduction and integration into microsystems. Currently InGaAsN, on a GaAs substrate, is being commercially pursued for the important 1.3 micrometer dispersion minima of silica-glass optical fiber; due, in large part, to previous research at Sandia National Laboratories. However, InGaAsN has not shown great promise for 1.55 micrometer emission which is the low-loss window of single mode optical fiber used in transatlantic fiber. Other important applications for the antimonide/nitride based materials include the base junction of an HBT to reduce the operating voltage which is important for wireless communication links, and for improving the efficiency of a multijunction solar cell. We have undertaken the first comprehensive theoretical, experimental and device study of this material with promising results. Theoretical modeling has identified GaAsSbN to be a similar or potentially superior candidate to InGaAsN for long wavelength emission on GaAs. We have confirmed these predictions by producing emission out to 1.66 micrometers and have achieved edge emitting and VCSEL electroluminescence at 1.3 micrometers. We have also done the first study of the transport properties of this material including mobility, electron/hole mass, and exciton reduced mass. This study has increased the understanding of the III-antimonide/nitride materials enough to warrant consideration for all of the target device applications.

In a superposition of quantum states, a bit can be in both the states '0' and '1' at the same time. This feature of the quantum bit or qubit has no parallel in classical systems. Currently, quantum computers consisting of 4 to 7 qubits in a 'quantum computing register' have been built. Innovative algorithms suited to quantum computing are now beginning to emerge, applicable to sorting and cryptanalysis, and other applications. A framework for overcoming slightly inaccurate quantum gate interactions and for causing quantum states to survive interactions with surrounding environment is emerging, called quantum error correction. Thus there is the potential for rapid advances in this field. Although quantum information processing can be applied to secure communication links (quantum cryptography) and to crack conventional cryptosystems, the first few computing applications will likely involve a 'quantum computing accelerator' similar to a 'floating point arithmetic accelerator' interfaced to a conventional Von Neumann computer architecture. This research is to develop a roadmap for applying Sandia's capabilities to the solution of some of the problems associated with maintaining quantum information, and with getting data into and out of such a 'quantum computing accelerator'. We propose to focus this work on 'quantum I/O technologies' by applying quantum optics on semiconductor nanostructures to leverage Sandia's expertise in semiconductor microelectronic/photonic fabrication techniques, as well as its expertise in information theory, processing, and algorithms. The work will be guided by understanding of practical requirements of computing and communication architectures. This effort will incorporate ongoing collaboration between 9000, 6000 and 1000 and between junior and senior personnel. Follow-on work to fabricate and evaluate appropriate experimental nano/microstructures will be proposed as a result of this work.

GaAsSbN was grown by organometallic vapor phase epitaxy (OMVPE) as an alternative material to InGaAsN for long wavelength emission on GaAs substrates. OMVPE of GaAsSbN using trimethylgallium, 100% arsine, trimethylantimony, and 1,1-dimethylhydrazine was found to be kinetically limited at growth temperatures ranging from 520 C to 600 C, with an activation energy of 10.4 kcal/mol. The growth rate was linearly dependent on the group III flow and has a complex dependence on the group V constituents. A room temperature photoluminescence wavelength of >1.3 {micro}m was observed for unannealed GaAs{sub 0.69}Sb{sub 0.3}N{sub 0.01}. Low temperature (4 K) photoluminescence of GaAs{sub 0.69}Sb{sub 0.3}N{sub 0.01} shows an increase in FWHM of 2.4-3.4 times the FWHM of GaAs{sub 0.7}Sb{sub 0.3}, a red shift of 55-77 meV, and a decrease in intensity of one to two orders of magnitude. Hall measurements indicate a behavior similar to that of InGaAsN, a 300 K hole mobility of 350 cm{sup 2}/V-s with a 1.0 x 10{sup 17}/cm{sup 3} background hole concentration, and a 77 K mobility of 1220 cm{sup 2}/V-s with a background hole concentration of 4.8 x 10{sup 16}/cm{sup 3}. The hole mass of GaAs{sub 0.7}Sb{sub 0.3}/GaAs heterostructures was estimated at 0.37-0.40m{sub o}, and we estimate an electron mass of 0.2-0.3m{sub o} for the GaAs{sub 0.69}Sb{sub 0.3}N{sub 0.01}/GaAs system. The reduced exciton mass for GaAsSbN was estimated at about twice that found for GaAsSb by a comparison of diamagnetic shift vs. magnetic field.

We have developed force fields for the calculation of adsorption of NH{sub 3}, CO{sub 2}, and H{sub 2}O on zeolite 4A by performing Gibbs ensemble Monte Carlo simulations to fit experimental isotherms at 298 K. The calculated NH{sub 3} and CO{sub 2} isotherms are in excellent agreement with experimental data over a wide range of temperatures and several orders of magnitude in pressure. We have calculated isotherms for H{sub 2}O in 4A using two different models and have found that H{sub 2}O saturates zeolite 4A even at pressures as low as 0.01 kPa for the range of temperatures studied. We have studied the geometry of the adsorption sites and their dependence on loading. At low pressures, CO{sub 2} molecules adsorb with their longitudinal axis pointing toward the center of the supercage, whereas at higher pressures, the two oxygen atoms are equidistant from the Na atom in the binding site.

We present low-temperature (T = 4K) photoluminescence studies of the effect of adding nitrogen to 6-nm-wide single-strained GaAsSb quantum wells on GaAs. The samples were grown by both MBE and MOCVD techniques. The nominal Sb concentration is about 30%. Adding about 1 to 2% N drastically reduced the bandgap energies from 1 to 0.75 eV, or 1.20 to 1.64 μm. Upon performing ex situ rapid thermal anneals, 825°C for 10s, the band gap energies as well as the photoluminescence intensities increased. The intensities increased by an order of magnitude for the annealed samples and the band gap energies increased by about 50 - 100 meV, depending on growth temperatures. The photoluminescence linewidths tended to decrease upon annealing. Preliminary results of a first-principles band structure calculation for the GaAsSbN system are also presented.

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The authors discuss their new implementation of the Adaptive Coordinate Real-space Electronic Structure (ACRES) method for studying the atomic and electronic structure of infinite periodic as well as finite systems, based on density functional theory. This improved version aims at making the method widely applicable and efficient, using high performance Fortran on parallel architectures. The scaling of various parts of an ACRES calculation is analyzed and compared to that of plane-wave based methods. The new developments that lead to enhanced performance, and their parallel implementation, are presented in detail. They illustrate the application of ACRES to the study of elemental crystalline solids, molecules and complex crystalline materials, such as blue bronze and zeolites.

The optical gain spectra for GaInNAs/GaAs quantum wells are computed using a microscopic laser theory. From these spectra, the peak gain and carrier radiative decay rate as functions of carrier density are determined. These dependences allow the study of the lasing threshold current density of GaInNAs/GaAs quantum well structures.

The conduction band minimum formation of GaAs{sub 0.5{minus}y}P{sub 0.5{minus}y}N{sub 2y} is investigated for small nitrogen compositions (0.1% < 2y < 1.0%), by using a pseudopotential technique. This formation is caused by two unusual processes both involving the deep-gap impurity level existing in the dilute alloy limit y {r_arrow} 0. The first process is an anticrossing with the {Gamma}{sub Ic}-like extended state of GaAs{sub 0.5}P{sub 0.5}. The second process is an interaction with other impurity levels forming a subband. These two processes are expected to occur in any alloys exhibiting a deep-gap impurity level at one of its dilute limit.

Se-intercalated graphite compounds (Se-GICs) are considered as promising candidates for room-temperature thermoelectric cooling devices. Here the authors analyze the crystallographic structure and electronic properties of these materials within the framework of density-functional theory. First, the Adaptive-Coordinate Real-space Electronic Structure (ACRES) code is used to determine the stable structure of a representative stage-2 Se-GIC by relaxing atomic positions. The stable configuration is found to be a pendant-type structure, in which each selenium is bonded covalently to two atoms within the same carbon layer, causing a local distortion of the in-plane conjugation of the graphite. Then, they use the full potential linearized augmented plane wave (FP-LAPW) method to calculate the electronic band structure of the material and discuss its properties. Near the Fermi energy E{sub F}, there are wide bands originating from the host graphitic electronic structure and a few very narrow bands mainly of Se 4p character. The latter bands contribute to high peaks in the density of states close to E{sub F}. They show that this feature, although typical of many good thermoelectrics, does not necessarily imply high thermopower in the case of Se-GICs.

The authors report a measurement of the variation of the value of the linewidth of an excitonic transition in InGaAsN alloys (1 and 2% nitrogen) as a function of hydrostatic pressure using photoluminescence spectroscopy. The samples were grown by metal-organic chemical vapor deposition and the photoluminescence measurements were performed a 4K. The authors find that the value of the excitonic linewidth increases as a function of pressure until about 100 kbars after which it tends to saturate. This change in the excitonic linewidth is used to derive the pressure variation of the reduced mass of the exciton using a theoretical formalism which is based on the premise that the broadening of the excitonic transition is caused primarily by compositional fluctuations in a completely disordered alloy. The variation of the excitonic reduced mass thus derived is compared with that recently determined using a first-principles band structure calculation based on local density approximation.

The variation of the value of the linewidth of an excitonic transition in InGaAsN alloys (1% and 2% nitrogen) as a function of hydrostatic pressure using photoluminescence spectroscopy is studied at 4 K. The excitonic linewidth increases as a function of pressure until about 100 kbar after which it tends to saturate. This pressure dependent excitonic linewidth is used to derive the pressure variation of the exciton reduced mass using a theoretical formalism based on the premise that the broadening of the excitonic transition is caused primarily by compositional fluctuations in a completely disordered alloy. The linewidth derived ambient pressure masses are compared and found to be in agreement with other mass measurements. The variation of this derived mass is compared with the results from a nearly first-principles approach in which calculations based on the local density approximation to the Kohn-Sham density functional theory are corrected using a small amount of experimental input.

We discuss a recent investigation of adatom behavior on the AlSb(001) surface using first-principles electronic structure methods based on the density functional theory. For Al and Sb adatoms, we find a number of novel adatom structures that differ dramatically from previous results for the superficially similar group-III arsenides. In particular, we conclude that it is energetically favorable for an Al adatom to incorporate substitutionally into the outermost layer of the AlSb surface. This observation helps motivate a proposed new reconstruction for the AlSb(001) surface. Finally, we argue that the unusual adatom behavior identified for this surface probably results from the presence of a dimer row composed of a double layer of group-V atoms in the reconstruction, and therefore, it should be generic to all of the antimonides, as well as, the c(4 × 4) reconstruction of the arsenides and phosphides.