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.

Characterization and modeling of premixed turbulent n-heptane flames in the thin reaction zone regime

n-heptane/air premixed turbulent flames in the high-Karlovitz portion of the thin reaction zone regime are characterized and modeled in this thesis using Direct Numerical Simulations (DNS) with detailed chemistry. In order to perform these simulations, a time-integration scheme that can efficiently handle the stiffness of the equations solved is developed first. A first simulation with unity Lewis number is considered in order to assess the effect of turbulence on the flame in the absence of differential diffusion. A second simulation with non-unity Lewis numbers is considered to study how turbulence affects differential diffusion. In the absence of differential diffusion, minimal departure from the 1D unstretched flame structure (species vs. temperature profiles) is observed. In the non-unity Lewis number case, the flame structure lies between that of 1D unstretched flames with "laminar" non-unity Lewis numbers and unity Lewis number. This is attributed to effective Lewis numbers resulting from intense turbulent mixing and a first model is proposed. The reaction zone is shown to be thin for both flames, yet large chemical source term fluctuations are observed. The fuel consumption rate is found to be only weakly correlated with stretch, although local extinctions in the non-unity Lewis number case are well correlated with high curvature. These results explain the apparent turbulent flame speeds. Other variables that better correlate with this fuel burning rate are identified through a coordinate transformation. It is shown that the unity Lewis number turbulent flames can be accurately described by a set of 1D (in progress variable space) flamelet equations parameterized by the dissipation rate of the progress variable. In the non-unity Lewis number flames, the flamelet equations suggest a dependence on a second parameter, the diffusion of the progress variable. A new tabulation approach is proposed for the simulation of such flames with these dimensionally-reduced manifolds.

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.

The impact of physical processes on algal growth

Mixing and transport processes in surface waters strongly influence the structure of aquatic ecosystems. The impact of mixing on algal growth is species-dependent, affecting the competition among species and acting as a selective factor for the composition of the biocoenose. Were it not for the ever-changing ”aquatic weather”, the composition of pelagic ecosystems would be relatively simple. Probably just a few optimally adapted algal species would survive in a given water-body. In contrast to terrestrial ecosystems, in which the spatial heterogeneity is primarily responsible for the abundance of niches, in aquatic systems (especially in the pelagic zone) the niches are provided by the temporal structure of physical processes. The latter are discussed in terms of the relative sizes of physical versus biological time-scales. The relevant time-scales of mixing and transport cover the range between seconds and years. Correspondingly, their influence on growth of algae is based on different mechanisms: rapid changes are relevant for the fast biological processes such as nutrient uptake and photosynthesis, and the slower changes are relevant for the less dynamic processes such as growth, respiration, mineralization, and settling of algal cells. Mixing time-scales are combined with a dynamic model of photosynthesis to demonstrate their influence on algal growth.

Properties of convergence of a class of iterative processes generated by sequences of self-mappings with applications to switched dynamic systems

This article investigates the convergence properties of iterative processes involving sequences of self-mappings of metric or Banach spaces. Such sequences are built from a set of primary self-mappings which are either expansive or non-expansive self-mappings and some of the non-expansive ones can be contractive including the case of strict contractions. The sequences are built subject to switching laws which select each active self-mapping on a certain activation interval in such a way that essential properties of boundedness and convergence of distances and iterated sequences are guaranteed. Applications to the important problem of stability of dynamic switched systems are also given.

Quantum Simulation of Dissipative Processes without Reservoir Engineering

We present a quantum algorithm to simulate general finite dimensional Lindblad master equations without the requirement of engineering the system-environment interactions. The proposed method is able to simulate both Markovian and non-Markovian quantum dynamics. It consists in the quantum computation of the dissipative corrections to the unitary evolution of the system of interest, via the reconstruction of the response functions associated with the Lindblad operators. Our approach is equally applicable to dynamics generated by effectively non-Hermitian Hamiltonians. We confirm the quality of our method providing specific error bounds that quantify its accuracy.