First principles based multiparadigm modeling of electronic structures and dynamics

Electronic structures and dynamics are the key to linking the material composition and structure to functionality and performance.

An essential issue in developing semiconductor devices for photovoltaics is to design materials with optimal band gaps and relative positioning of band levels. Approximate DFT methods have been justified to predict band gaps from KS/GKS eigenvalues, but the accuracy is decisively dependent on the choice of XC functionals. We show here for CuInSe₂ and CuGaSe₂, the parent compounds of the promising CIGS solar cells, conventional LDA and GGA obtain gaps of 0.0-0.01 and 0.02-0.24 eV (versus experimental values of 1.04 and 1.67 eV), while the historically first global hybrid functional, B3PW91, is surprisingly the best, with band gaps of 1.07 and 1.58 eV. Furthermore, we show that for 27 related binary and ternary semiconductors, B3PW91 predicts gaps with a MAD of only 0.09 eV, which is substantially better than all modern hybrid functionals, including B3LYP (MAD of 0.19 eV) and screened hybrid functional HSE06 (MAD of 0.18 eV).

The laboratory performance of CIGS solar cells (> 20% efficiency) makes them promising candidate photovoltaic devices. However, there remains little understanding of how defects at the CIGS/CdS interface affect the band offsets and interfacial energies, and hence the performance of manufactured devices. To determine these relationships, we use the B3PW91 hybrid functional of DFT with the AEP method that we validate to provide very accurate descriptions of both band gaps and band offsets. This confirms the weak dependence of band offsets on surface orientation observed experimentally. We predict that the CBO of perfect CuInSe₂/CdS interface is large, 0.79 eV, which would dramatically degrade performance. Moreover we show that band gap widening induced by Ga adjusts only the VBO, and we find that Cd impurities do not significantly affect the CBO. Thus we show that Cu vacancies at the interface play the key role in enabling the tunability of CBO. We predict that Na further improves the CBO through electrostatically elevating the valence levels to decrease the CBO, explaining the observed essential role of Na for high performance. Moreover we find that K leads to a dramatic decrease in the CBO to 0.05 eV, much better than Na. We suggest that the efficiency of CIGS devices might be improved substantially by tuning the ratio of Na to K, with the improved phase stability of Na balancing phase instability from K. All these defects reduce interfacial stability slightly, but not significantly.

A number of exotic structures have been formed through high pressure chemistry, but applications have been hindered by difficulties in recovering the high pressure phase to ambient conditions (i.e., one atmosphere and room temperature). Here we use dispersion-corrected DFT (PBE-ulg flavor) to predict that above 60 GPa the most stable form of N₂O (the laughing gas in its molecular form) is a 1D polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03-0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions both polymers relax below 14 GPa to the same stable non-planar trans-polymer, accompanied by possible electronic structure transitions. The predicted phonon spectrum and dissociation kinetics validate the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a new type of conducting polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions.

Modeling non-adiabatic electron dynamics has been a long-standing challenge for computational chemistry and materials science, and the eFF method presents a cost-efficient alternative. However, due to the deficiency of FSG representation, eFF is limited to low-Z elements with electrons of predominant s-character. To overcome this, we introduce a formal set of ECP extensions that enable accurate description of p-block elements. The extensions consist of a model representing the core electrons with the nucleus as a single pseudo particle represented by FSG, interacting with valence electrons through ECPs. We demonstrate and validate the ECP extensions for complex bonding structures, geometries, and energetics of systems with p-block character (C, O, Al, Si) and apply them to study materials under extreme mechanical loading conditions.

Despite its success, the eFF framework has some limitations, originated from both the design of Pauli potentials and the FSG representation. To overcome these, we develop a new framework of two-level hierarchy that is a more rigorous and accurate successor to the eFF method. The fundamental level, GHA-QM, is based on a new set of Pauli potentials that renders exact QM level of accuracy for any FSG represented electron systems. To achieve this, we start with using exactly derived energy expressions for the same spin electron pair, and fitting a simple functional form, inspired by DFT, against open singlet electron pair curves (H₂ systems). Symmetric and asymmetric scaling factors are then introduced at this level to recover the QM total energies of multiple electron pair systems from the sum of local interactions. To complement the imperfect FSG representation, the AMPERE extension is implemented, and aims at embedding the interactions associated with both the cusp condition and explicit nodal structures. The whole GHA-QM+AMPERE framework is tested on H element, and the preliminary results are promising.

Observations and Modeling of Tropical Planetary Atmospheres

This thesis is a comprised of three different projects within the topic of tropical atmospheric dynamics. First, I analyze observations of thermal radiation from Saturn’s atmosphere and from them, determine the latitudinal distribution of ammonia vapor near the 1.5-bar pressure level. The most prominent feature of the observations is the high brightness temperature of Saturn’s subtropical latitudes on either side of the equator. After comparing the observations to a microwave radiative transfer model, I find that these subtropical bands require very low ammonia relative humidity below the ammonia cloud layer in order to achieve the high brightness temperatures observed. We suggest that these bright subtropical bands represent dry zones created by a meridionally overturning circulation.

Second, I use a dry atmospheric general circulation model to study equatorial superrotation in terrestrial atmospheres. A wide range of atmospheres are simulated by varying three parameters: the pole-equator radiative equilibrium temperature contrast, the convective lapse rate, and the planetary rotation rate. A scaling theory is developed that establishes conditions under which superrotation occurs in terrestrial atmospheres. The scaling arguments show that superrotation is favored when the off-equatorial baroclinicity and planetary rotation rates are low. Similarly, superrotation is favored when the convective heating strengthens, which may account for the superrotation seen in extreme global-warming simulations.

Third, I use a moist slab-ocean general circulation model to study the impact of a zonally-symmetric continent on the distribution of monsoonal precipitation. I show that adding a hemispheric asymmetry in surface heat capacity is sufficient to cause symmetry breaking in both the spatial and temporal distribution of precipitation. This spatial symmetry breaking can be understood from a large-scale energetic perspective, while the temporal symmetry breaking requires consideration of the dynamical response to the heat capacity asymmetry and the seasonal cycle of insolation. Interestingly, the idealized monsoonal precipitation bears resemblance to precipitation in the Indian monsoon sector, suggesting that this work may provide insight into the causes of the temporally asymmetric distribution of precipitation over southeast Asia.

Using Earth Deformation Caused by Surface Mass Loading to Constrain the Elastic Structure of the Crust and Mantle

Surface mass loads come in many different varieties, including the oceans, atmosphere, rivers, lakes, glaciers, ice caps, and snow fields. The loads migrate over Earth's surface on time scales that range from less than a day to many thousand years. The weights of the shifting loads exert normal forces on Earth's surface. Since the Earth is not perfectly rigid, the applied pressure deforms the shape of the solid Earth in a manner controlled by the material properties of Earth's interior. One of the most prominent types of surface mass loading, ocean tidal loading (OTL), comes from the periodic rise and fall in sea-surface height due to the gravitational influence of celestial objects, such as the moon and sun. Depending on geographic location, the surface displacements induced by OTL typically range from millimeters to several centimeters in amplitude, which may be inferred from Global Navigation and Satellite System (GNSS) measurements with sub-millimeter precision. Spatiotemporal characteristics of observed OTL-induced surface displacements may therefore be exploited to probe Earth structure. In this thesis, I present descriptions of contemporary observational and modeling techniques used to explore Earth's deformation response to OTL and other varieties of surface mass loading. With the aim to extract information about Earth's density and elastic structure from observations of the response to OTL, I investigate the sensitivity of OTL-induced surface displacements to perturbations in the material structure. As a case study, I compute and compare the observed and predicted OTL-induced surface displacements for a network of GNSS receivers across South America. The residuals in three distinct and dominant tidal bands are sub-millimeter in amplitude, indicating that modern ocean-tide and elastic-Earth models well predict the observed displacement response in that region. Nevertheless, the sub-millimeter residuals exhibit regional spatial coherency that cannot be explained entirely by random observational uncertainties and that suggests deficiencies in the forward-model assumptions. In particular, the discrepancies may reveal sensitivities to deviations from spherically symmetric, non-rotating, elastic, and isotropic (SNREI) Earth structure due to the presence of the South American craton.

A modeling approach to identify optimal habitat and suitable fishing grounds for neon flying squid (Ommastrephes bartramii) in the Northwest Pacific Ocean

We developed a habitat suitability index (HSI) model to understand and identify the optimal habitat and potential fishing grounds for neon f lying squid (Ommastrephes bartramii) in the Northwest Pacific Ocean. Remote sensing data, including sea surface temperature, sea surface salinity, sea surface height, and chlorophyll-a concentrations, as well as fishery data from Chinese mainland squid f leets in the main fishing ground (150–165°E longitude) from August to October, from 1999 to 2004, were used. The HSI model was validated by using fishery data from 2005. The arithmetic mean modeling with three of the environmental variables—sea surface temperature, sea surface height anomaly, and chlorophyll- a concentrations—was defined as the most parsimonious HSI model. In 2005, monthly HSI values >0.6 coincided with productive fishing grounds and high fishing effort from August to October. This result implies that the model can reliably predict potential f ishing grounds for O. bartramii. Because spatially explicit fisheries and environmental data are becoming readily available, it is feasible to develop a dynamic, near real-time habitat model for improving the process of identifying potential fishing areas for and optimal habitats of neon flying squid.

Age validation, growth modeling, and mortality estimates for striped trumpeter (Latris lineata) from southeastern Australia: making the most of patchy data

Age estimates for striped trumpeter (Latris lineata) from Tasmanian waters were produced by counting annuli on the transverse section of sagittal otoliths and were validated by comparison of growth with known-age individuals and modal progression of a strong recruitment pulse. Estimated ages ranged from one to 43 years; fast growth rates were observed for the first five years. Minimal sexual dimorphism was shown to exist between length, weight, and growth characteristics of striped trumpeter. Seasonal growth variability was strong in individuals up to at least age four, and growth rates peaked approximately one month after the observed peak in sea surface temperature. A modified two-phase von Bertalanffy growth function was fitted to the length-at-age data, and the transition between growth phases was linked to apparent changes in physiological and life history traits, including offshore movement as fish approach maturity. The two-phase curve was found to represent the mean length at age in the data better than the standard von Bertalanffy growth function. Total mortality was estimated by using catch curve analysis based on the standard and two-phase von Bertalanffy growth functions, and estimates of natural mortality were calculated by using two empirical models, one based on longevity and the other based on the parameters L∞ and k from both growth functions. The interactions between an inshore gillnet fishery targeting predominately juveniles and an offshore hook fishery targeting predominately adults highlight the need to use a precautionary approach when developing harvest strategies.

Modeling North Pacific temperature and pressure changes from coastal tree-ring chronologies

Climate modeling using coastal tree-ring chronologies has yielded the first summer temperature reconstructions for coastal stations along the Gulf of Alaska and the Pacific Northwest. These land temperature reconstructions are strongly correlated with nearby sea surface temperatures, indicating large-scale ocean-atmospheric influences. Significant progress has also been made in modeling winter land temperatures and sea surface temperatures from coastal and shipboard stations. In addition to temperature, the pressure variability center over the central North Pacific Ocean (PAC), which is related to the strength and location of the Aleutian Low pressure system, could be extended using coastal tree rings.

Unsteady transition in an axial-flow turbine. Part 2. Cascade measurements and modeling

Part 1 of this paper reanalyzed previously published measurements from the rotor of a low-speed, single-stage, axial-flow turbine, which highlighted the unsteady nature of the suction surface transition process. Part 2 investigates the significance of the wake jet and the unsteady frequency parameter. Supporting experiments carried out in a linear cascade with varying inlet turbulence are described, together with a simple unsteady transition model explaining the features of seen in the turbine.

Modeling of unsteady transitional boundary layers

In turbomachinery, a considerable proportion of the blade surface area can be covered by transitional boundary layers. This means that accurate prediction of the profile loss and boundary layer behavior in general depends on the accurate modeling of the transitional boundary layers, especially at low Reynolds numbers. This paper presents a model for determining the intermittency resulting from the unsteady transition caused by the passage of wakes over a blade surface. The model is founded on work by Emmons (1951) who showed that the intermittency could be calculated from a knowledge of the behavior of randomly formed turbulent spots. The model is used to calculate the development of the boundary layer on the rotor of a low Reynolds number single-stage turbine. The predictions are compared with experimental results obtained using surface-mounted hot-film anemometers and hot-wire traverses of the rotor midspan boundary layer at two different rotor-stator gaps. The validity and limitations of the model are discussed.

Trimeresurus stejnegeri snake venom plasminogen activator - Site-directed mutagenesis and molecular modeling

The specific plasminogen activator from Trimeresurus stejnegeri venom (TSV-PA) is a serine proteinase presenting 23% sequence identity with the proteinase domain of tissue type plasminogen activator, and 63% with batroxobin, a fibrinogen clotting enzyme from Bothrops atrox venom that does not activate plasminogen. TSV-PA contains six disulfide bonds and has been successfully overexpressed in Escherichia coli (Zhang, Y., Wisner, A., Xiong, Y. L,, and Bon, C, (1995) J. Biol. Chem. 270, 10246-10255), To identify the functional domains of TSV-PA, we focused on three short peptide fragments of TSV-PA showing important sequence differences with batroxobin and other venom serine proteinases. Molecular modeling shows that these sequences are located in surface loop regions, one of which is next to the catalytic site, When these sequences were replaced in TSV-PA by the equivalent batroxobin residues none generated either fibrinogen-clotting or direct fibrinogenolytic activity, Two of the replacements had little effect in general and are not critical to the specificity of TSV-PA for plasminogen. Nevertheless, the third replacement, produced by the conversion of the sequence DDE 96a-98 to NVI, significantly increased the K-m for some tripeptide chromogenic substrates and resulted in undetectable plasminogen activation, indicating the key role that the sequence plays in substrate recognition by the enzyme.

Characterize dynamic conformational space of human CCR5 extracellular domain by molecular modeling and molecular dynamics simulation

The chemokine receptor CCR5 is the receptor for several chemokines and major coreceptor for R5 human immunodeficiency virus type-1 strains entry into cell. Three-dimensional models of CCR5 were built by using homology modeling approach and 1 ns molecular dynamics (MD) simulation, because studies of site-directed mutagenesis and chimeric receptors have indicated that the N-terminus (Nt) and extracellular loops (ECLs) of CCR5 are important for ligands binding and viral fusion and entry, special attention was focused on disulfide bond function, conformational flexibility, hydrogen bonding, electrostatic interactions, and solvent-accessible surface area of Nt and ECLs of this protein part. We found that the extracellular segments of CCR5 formed a well-packet globular domain with complex interactions occurred between them in a majority of time of MID simulation, but Nt region could protrude from this domain sometimes. The disulfide bond Cys20-Cys269 is essential in controlling specific orientation of Nt region and maintaining conformational integrity of extracellular domain. RMS comparison analysis between conformers revealed the ECL1 of CCR5 stays relative rigid, whereas the ECL2 and Nt are rather flexible. Solvent-accessible surface area calculations indicated that the charged residues within Nt and ECL2 are often exposed to solvent. Integrating these results with available experimental data, a two-step gp120-CCR5 binding mechanism was proposed. The dynamic interaction of CCR5 extracellular domain with gp120 was emphasized. (C) 2004 Elsevier B.V. All rights reserved.

Modeling fatigue crack growth in crystalline solids with discrete dislocation plasticity

Analyses of crack growth under cyclic loading conditions are discussed where plastic flow arises from the motion of large numbers of discrete dislocations and the fracture properties are embedded in a cohesive surface constitutive relation. The formulation is the same as used to analyse crack growth under monotonic loading conditions, differing only in the remote loading being a cyclic function of time. Fatigue, i.e. crack growth in cyclic loading at a driving force for which the crack would have arrested under monotonic loading, emerges in the simulations as a consequence of the evolution of internal stresses associated with the irreversibility of the dislocation motion. A fatigue threshold, Paris law behaviour, striations, the accelerated growth of short cracks and the scaling with material properties are outcomes of the calculations. Results for single crystals and polycrystals will be discussed.

Optimized vertical carbon nanotube forests for multiplex surface-enhanced raman scattering detection

The highly sensitive and molecule-specific technique of surface-enhanced Raman spectroscopy (SERS) generates high signal enhancements via localized optical fields on nanoscale metallic materials, which can be tuned by manipulation of the surface roughness and architecture on the submicrometer level. We investigate gold-functionalized vertically aligned carbon nanotube forests (VACNTs) as low-cost straightforward SERS nanoplatforms. We find that their SERS enhancements depend on their diameter and density, which are systematically optimized for their performance. Modeling of the VACNT-based SERS substrates confirms consistent dependence on structural parameters as observed experimentally. The created nanostructures span over large substrate areas, are readily configurable, and yield uniform and reproducible SERS enhancement factors. Further fabricated micropatterned VACNTs platforms are shown to deliver multiplexed SERS detection. The unique properties of CNTs, which can be synergistically utilized in VACNT-based substrates and patterned arrays, can thus provide new generation platforms for SERS detection. © 2012 American Chemical Society.

Development of a new apparatus for modeling deep excavation related problems in geotechnical centrifuge

Underground space is commonly exploited both to maximise the utility of costly land in urban development and to reduce the vertical load acting on the ground. Deep excavations are carried out to construct various types of underground infrastructure such as deep basements, subways and service tunnels. Although the soil response to excavation is known in principle, designers lack practical calculation methods for predicting both short- and long-term ground movements. As the understanding of how soil behaves around an excavation in both the short and long term is insufficient and usually empirical, the judgements used in design are also empirical and serious accidents are common. To gain a better understanding of the mechanisms involved in soil excavation, a new apparatus for the centrifuge model testing of deep excavations in soft clay has been developed. This apparatus simulates the field construction sequence of a multi-propped retaining wall during centrifuge flight. A comparison is given between the new technique and the previously used method of draining heavy fluid to simulate excavation in a centrifuge model. The new system has the benefit of giving the correct initial ground conditions before excavation and the proper earth pressure distribution on the retaining structures during excavation, whereas heavy fluid only gives an earth pressure coefficient of unity and is unable to capture any changes in the earth pressure coefficient of soil inside the zone of excavation, for example owing to wall movements. Settlements of the ground surface, changes in pore water pressure, variations in earth pressure, prop forces and bending moments in the retaining wall are all monitored during excavation. Furthermore, digital images taken of a cross-section during the test are analysed using particle image velocimetry to illustrate ground deformation and soil–structure interaction mechanisms. The significance of these observations is discussed.

Strategies for modeling turbulent flows in electronics

Hybrid methods based on the Reynolds Averaged Navier Stokes (RANS) equations and the Large Eddy Simulation (LES) formulation are investigated to try and improve the accuracy of heat transfer and surface temperature predictions for electronics systems and components. Two relatively low Reynolds number flows are studied using hybrid RANS-LES, RANS-Implicit-LES (RANS-ILES) and non-linear LES models. Predictions using these methods are in good agreement with each other, even using different grid resolutions. © 2008 IEEE.

Modeling cyclic behavior of lightly overconsolidated clays in simple shear

Assessment of seismic performance and estimation of permanent displacements for submerged slopes require the accurate description of the soil's stress-strain-strength relationship under irregular cyclic loading. The geological profile of submerged slopes on the continental shelf typically consists of normally to lightly overconsolidated clays with depths ranging from a few meters to a few hundred meters and very low slope angles. This paper describes the formulation of a simplified effective-stress-based model, which is able to capture the key aspects of the cyclic behavior of normally consolidated clays. The proposed constitutive law incorporates anisotropic hardening and bounding surface principles to allow the user to simulate different shear strain and stress reversal histories as well as provide realistic descriptions of the accumulation of plastic shear strains and excess pore pressure during successive loading cycles. (C) 2000 Published by Elsevier Science Ltd. | Assessment of seismic performance and estimation of permanent displacements for submerged slopes require the accurate description of the soil's stress-strain-strength relationship under irregular cyclic loading. The geological profile of submerged slopes on the continental shelf typically consists of normally to lightly overconsolidated clays with depths ranging from a few meters to a few hundred meters and very low slope angles. This paper describes the formulation of a simplified effective-stress-based model, which is able to capture the key aspects of the cyclic behavior of normally consolidated clays. The proposed constitutive law incorporates anisotropic hardening and bounding surface principles to allow the user to simulate different shear strain and stress reversal histories as well as provide realistic descriptions of the accumulation of plastic shear strains and excess pore pressures during successive loading cycles.