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.

Battery-Powered RF Pre-Ionization System for the Caltech Magnetohydrodynamically-Driven Jet Experiment: RF Discharge Properties and MHD-Driven Jet Dynamics

This thesis describes investigations of two classes of laboratory plasmas with rather different properties: partially ionized low pressure radiofrequency (RF) discharges, and fully ionized high density magnetohydrodynamically (MHD)-driven jets. An RF pre-ionization system was developed to enable neutral gas breakdown at lower pressures and create hotter, faster jets in the Caltech MHD-Driven Jet Experiment. The RF plasma source used a custom pulsed 3 kW 13.56 MHz RF power amplifier that was powered by AA batteries, allowing it to safely float at 4-6 kV with the cathode of the jet experiment. The argon RF discharge equilibrium and transport properties were analyzed, and novel jet dynamics were observed.

Although the RF plasma source was conceived as a wave-heated helicon source, scaling measurements and numerical modeling showed that inductive coupling was the dominant energy input mechanism. A one-dimensional time-dependent fluid model was developed to quantitatively explain the expansion of the pre-ionized plasma into the jet experiment chamber. The plasma transitioned from an ionizing phase with depressed neutral emission to a recombining phase with enhanced emission during the course of the experiment, causing fast camera images to be a poor indicator of the density distribution. Under certain conditions, the total visible and infrared brightness and the downstream ion density both increased after the RF power was turned off. The time-dependent emission patterns were used for an indirect measurement of the neutral gas pressure.

The low-mass jets formed with the aid of the pre-ionization system were extremely narrow and collimated near the electrodes, with peak density exceeding that of jets created without pre-ionization. The initial neutral gas distribution prior to plasma breakdown was found to be critical in determining the ultimate jet structure. The visible radius of the dense central jet column was several times narrower than the axial current channel radius, suggesting that the outer portion of the jet must have been force free, with the current parallel to the magnetic field. The studies of non-equilibrium flows and plasma self-organization being carried out at Caltech are relevant to astrophysical jets and fusion energy research.

Dynamics of the East Asian Summer Monsoon in Present and Future Climates

This thesis aims at enhancing our fundamental understanding of the East Asian summer monsoon (EASM), and mechanisms implicated in its climatology in present-day and warmer climates. We focus on the most prominent feature of the EASM, i.e., the so-called Meiyu-Baiu (MB), which is characterized by a well-defined, southwest to northeast elongated quasi-stationary rainfall band, spanning from eastern China to Japan and into the northwestern Pacific Ocean in June and July.

We begin with an observational study of the energetics of the MB front in present-day climate. Analyses of the moist static energy (MSE) budget of the MB front indicate that horizontal advection of moist enthalpy, primarily of dry enthalpy, sustains the front in a region of otherwise negative net energy input into the atmospheric column. A decomposition of the horizontal dry enthalpy advection into mean, transient, and stationary eddy fluxes identifies the longitudinal thermal gradient due to zonal asymmetries and the meridional stationary eddy velocity as the most influential factors determining the pattern of horizontal moist enthalpy advection. Numerical simulations in which the Tibetan Plateau (TP) is either retained or removed show that the TP influences the stationary enthalpy flux, and hence the MB front, primarily by changing the meridional stationary eddy velocity, with reinforced southerly wind on the northwestern flank of the north Pacific subtropical high (NPSH) over the MB region and northerly wind to its north. Changes in the longitudinal thermal gradient are mainly confined to the near downstream of the TP, with the resulting changes in zonal warm air advection having a lesser impact on the rainfall in the extended MB region.

Similar mechanisms are shown to be implicated in present climate simulations in the Couple Model Intercomparison Project - Phase 5 (CMIP5) models. We find that the spatial distribution of the EASM precipitation simulated by different models is highly correlated with the meridional stationary eddy velocity. The correlation becomes more robust when energy fluxes into the atmospheric column are considered, consistent with the observational analyses. The spread in the area-averaged rainfall amount can be partially explained by the spread in the simulated globally-averaged precipitation, with the rest primarily due to the lower-level meridional wind convergence. Clear relationships between precipitation and zonal and meridional eddy velocities are observed.

Finally, the response of the EASM to greenhouse gas forcing is investigated at different time scales in CMIP5 model simulations. The reduction of radiative cooling and the increase in continental surface temperature occur much more rapidly than changes in sea surface temperatures (SSTs). Without changes in SSTs, the rainfall in the monsoon region decreases (increases) over ocean (land) in most models. On longer time scales, as SSTs increase, rainfall changes are opposite. The total response to atmospheric CO^2 forcing and subsequent SST warming is a large (modest) increase in rainfall over ocean (land) in the EASM region. Dynamic changes, in spite of significant contributions from the thermodynamic component, play an important role in setting up the spatial pattern of precipitation changes. Rainfall anomalies over East China are a direct consequence of local land-sea contrast, while changes in the larger-scale oceanic rainfall band are closely associated with the displacement of the larger-scale NPSH. Numerical simulations show that topography and SST patterns play an important role in rainfall changes in the EASM region.

Lurking in ULIRGs: Molecular Gas in local Merging Galaxies

Mergers and interacting galaxies are pivotal to the evolution of galaxies in the universe. They are the sites of prodigious star formation and key to understanding the starburst processes: the physical and chemical properties and the dynamics of the molecular gas. ULIRGs or Ultraluminous Infrared Galaxies are a result of many of these mergers. They host extreme starbursts, AGNs, and mergers. They are the perfect laboratory to probe the connection between starbursts, black hole accretion and mergers and to further our understanding of star formation and merging.

NGC 6240 and Arp 220 can be considered the founding members of this very active class of objects. They are in different stages of merging and hence are excellent case studies to further our understanding about the merging process. We have imaged the dense star-forming regions of these galaxies at sub-arcsec resolution with CARMA C and B Configurations (2" and 0.5 - 0.8"). Multi-band imaging allows excitation analysis of HCN, HCO⁺, HNC, and CS along with CO transitions to constrain the properties of the gas. Our dataset is unique in that we have observed these lines at similar resolutions and high sensitivity which can be used to derive line ratios of faint high excitation lines.

Arp 220 has not had confirmed X-ray AGN detections for either nuclei. However, our observations indicate HCN/HNC ratios consistent with the chemistry of X-ray Dominated Regions (XDRs) -- a likely symptom of AGN. We calculated the molecular Hydrogen densities using each of the molecular species and conclude that assuming abundances of HNC and HCO⁺ similar to those in galactic sources are incorrect in the case of ULIRGs. The physical conditions in the dense molecular gas in ULIRGs alter these abundances. The derived H2 volume densities are ~ 5 x 10⁴ cm^-3 in both Arp 220 nuclei and ~ 10⁴ cm^-3 in NGC 6240.

Chemical Reaction Dynamics of the Liquid/Vapor Interface Studied by Mass Spectrometry

This thesis presents investigations of chemical reactions occurring at the liquid/vapor interface studied using novel sampling methodologies coupled with detection by mass spectrometry. Chapters 2 and 3 utilize the recently developed technique of field-induced droplet ionization mass spectrometry (FIDI-MS), in which the application of a strong electric field to a pendant microliter droplet results in the ejection of highly charged progeny droplets from the liquid surface. In Chapter 2, this method is employed to study the base-catalyzed dissociation of a surfactant molecule at the liquid/vapor interface upon uptake of ammonia from the gas phase. This process is observed to occur without significant modulation of the bulk solution pH, suggesting a transient increase in surface pH following the uptake of gaseous ammonia. Chapter 3 presents real-time studies of the oxidation of the model tropospheric organic compound glycolaldehyde by photodissociation of iron (III) oxalate complexes. The oxidation products of glycolaldehyde formed in this process are identified, and experiments in a deoxygenated environment identify the role of oxygen in the oxidation pathway and in the regeneration of iron (III) following photo-initiated reduction. Chapter 4 explores alternative methods for the study of heterogeneous reaction processes by mass spectrometric sampling from liquid surfaces. Bursting bubble ionization (BBI) and interfacial sampling with an acoustic transducer (ISAT) generate nanoliter droplets from a liquid surface that can be sampled via the atmospheric pressure interface of a mass spectrometer. Experiments on the oxidation of oleic acid by ozone using ISAT are also presented. Chapters 5 and 6 detail mechanistic studies and applications of free-radical-initiated peptide sequencing (FRIPS), a technique employing gas-phase free radical chemistry to the sequencing of peptides and proteins by mass spectrometry. Chapter 5 presents experimental and theoretical studies on the anomalous mechanism of dissociation observed in the presence of serine and threonine residues in peptides. Chapter 6 demonstrates the combination of FRIPS with ion mobility-mass spectrometry (IM-MS) for the separation of isomeric peptides.