80 research outputs found
From Fundamentals to Spectroscopic Applications of Density Functional Theory
Density functional theory (DFT) and its time-dependent counterpart (TDDFT) are crucial tools in material discovery, drug design, biochemistry, catalysis, and nanoscience. However, despite its exact theoretical basis, approximations are necessary throughout, from the description of electron exchange and correlation (xc) interactions to the representation of wavefunctions for
ever larger systems and the use of calculated quantities to explain and predict real-world phenomena. To address long-standing problems related to the speed and accuracy of approximations to the xc functional, we develop neural networks to emulate two such approximations, the local density (LDA) and generalized gradient (PBE) approximations, within the DFT code gpaw. We
present a strategy for retraining the network and assess which training data is necessary to optimize performance for total energies over a wide class of molecules and crystals. While certain classes of materials proved difficult to describe, neural network implementations were able to reproduce the LDA and PBE xc functionals with high accuracy and a reasonable computation time. In an effort to develop a more efficient, robust, and accurate method for predicting the optical properties of low-dimensional systems, we introduce the LCAO-TDDFT-k-ω code within gpaw, where a linear combination of atomic orbitals (LCAO) representation of the Kohn-Sham wavefunctions and TDDFT implementation in wavenumber k and frequency ω space provides substantial memory and time savings, and a first order derivative discontinuity correction to the electronic gap brings the optical spectra in line with experimental measurements. Convergence of the basis set, the use of low-dimensional response functions, and different ways to incorporate the energy correction are explored for a series of materials across all dimensions: 0D fullerene and chlorophyll monomers, 1D single-walled carbon nanotubes, 2D graphene and phosphorene monolayers, and 3D anatase and rutile titanium dioxide. We develop a set of visualization tools for resolving the energetic, spatial, and reciprocal space distributions of excitations, and find LCAO-TDDFT-k-ω yields qualitative and semi-quantitative agreement with other TDDFT methods and implementations at a fraction of the time and memory cost. Finally, we introduce a phenomenological hydrodynamic model for the optical conductivity of graphene, with contributions due to universal conductivity, Pauli blocking, and intraband transitions included in a systematic way, is fit empirically with results from TDDFT, and manages to reproduce experimental spectra across a wide range of energies within energy loss equations derived for 2D materials. We find experimental parameters such as the amount of doping in graphene, the size of the collection aperture, and the energy of incoming electrons influence the shape of the spectra in important ways, especially in the energy region accessible to higher resolution probing techniques
An optically stimulated superconducting-like phase in K3C60 far above equilibrium Tc
The control of non-equilibrium phenomena in complex solids is an important
research frontier, encompassing new effects like light induced
superconductivity. Here, we show that coherent optical excitation of molecular
vibrations in the organic conductor K3C60 can induce a non-equilibrium state
with the optical properties of a superconductor. A transient gap in the real
part of the optical conductivity and a low-frequency divergence of the
imaginary part are measured for base temperatures far above equilibrium Tc=20
K. These findings underscore the role of coherent light fields in inducing
emergent order.Comment: 40 pages, 23 figure
First-principles informed phenomenological models of optical and lattice response in materials
In this dissertation, we present work on the first-principles informed phenomenological modeling of the optical properties of materials. We use density functional theory and time-dependent density functional theory calculations to inform parameterized models of the response to light in materials. We include the effect of ultrafast nonequilibrium effects, as well as the importance of quantum mechanical lattice vibrations. Using these models, we validate the approaches, and predict the effect of both ultrafast phenomena as well as quantum mechanical vibrations on the optical properties of bulk and 2D materials. Such modeling opens up avenues for efficient phenomenological approaches to describing optical phenomena in materials while keeping the accuracy of first-principles simulations
Exploring graphitic carbon nitrides for (opto)electronic applications
Graphitische Karbonitride sind organische, kovalent gebundene, geschichtete und
kristalline Halbleiter mit einer hohen thermischen und chemischen Stabilität. Diese
Eigenschaften machen 2D Schichten der graphitischen Kristalle potentiell nĂĽtzlich
fĂĽr das Ziel, Limitationen von organischen 0D Molekularen und 1D polymerischen
Halbleitern zu ĂĽberwinden. Trotz dieser interessanten Eigenschaften haben nur
wenige Publikationen erfolgreich graphitische Karbonitride in optoelektronischen
Bauteilen eingesetzt. Um die Vorteile dieser Materialien nutzbar zu machen, wurden
bessere Synthesebedingungen gesucht. Die Verwendung von einem Iod-Eutektikum
zeigt, dass Anionen mit einem größeren Radius als Bromid nicht für die Stabilisation
von graphitischen Karbonitriden geeignet sind. Das Optimieren der
Synthesebedingungen von Poly(triazin-imid)-LiBr resultiert in der Reduzierung
von einem kohlenstoffreichen Zersetzungsprodukt bei vollständiger Kondensation.
Das Untersuchen der elektronischen Struktur mit ab initio Berechnungen ergibt,
dass der elektronische VB-CB-Ăśbergang verboten ist. Dies resultiert daraus, dass die
Zustände des obersten Valenzbandes nichtbindender Natur sind. Ein Band aus
nichtbindenden Elektronen als oberstes Valenzband ist vor allem aus „lone-pair
semiconductors“ aus der sechsten Hauptgruppe bekannt. In der Welt organischer
Halbleiter wurde dieses Phänomen bisher nicht beobachtet. Die geringe
makroskopische elektrische Leitfähigkeit der PTI-Filme wurde
mit der Leitfähigkeit auf Nanoebene verglichen, woraus gefolgert
werden kann, dass der Ladungsträgertransport durch den nanokristallinen
Charakter an den Kristall-Kristall Übergängen gestört wird. Die elektronische Leitfähigkeit, Mobilität der Ladungsträger sowie die Ladungsträgerdichte wurden untersucht. Die Energie Niveaus legen nahe das Elektronentransport in der Präsenz von Sauerstoff möglich ist. Die erste Applikation eines kovalenten organischen Netzwerks in
einer organischen lichtemittierenden Diode ist gezeigt worden.Graphitic carbon nitrides are organic covalently-bonded, layered, and crystalline
semiconductors with high thermal and oxidative stability. These properties make
2D layers of graphitic carbon nitrides potentially useful in overcoming the
limitations of 0D molecular and 1D polymer semiconductors. Only few
reports have shown them being employed in optoelectronic applications. With the
goal to find better reaction conditions that enable higher product quality from the
ionothermal synthesis the size effect of anions is studied by using an iodide eutectic
instead of bromide or chloride eutectic. The highest crystalline condensation
product obtained is melem, revealing that the large iodide anion is not capable of
stabilizing a graphitic structure. Studying the synthesis conditions of poly(triazine
imide) (PTI), the best characterized graphitic carbon nitride in literature, it is
revealed that the brown discoloration of the product is due to a carbon rich side
product. Reduction of reaction temperature and increase of reaction time allows
omittance of carbonisation. Analyzing the electronic structure with ab initio
calculations one finds that the lowest energy electronic transition in PTI is forbidden
due to a non-bonding uppermost valence band. A uppermost non-bonding valence
band is most reminiscent of lone-pair semiconductors and unknown in the world of
organic semiconductors making PTI the first organic lone-pair semiconductor. The
low electrical conductivity of PTI derivatives is compared to
nanoscale conductivity values. The results indicate that macroscopic conductivity is
hampered by the nano-crystalline character due to charge carrier trapping at crystal
interfaces. The effective mobility is in the range of amorphous organic
semiconductors with an unexpectedly high carrier density. The energy levels in PTI-LiBr potentially
enable environmentally stable n-transport. The first successful Application of a covalent organic framework in a
organic light emitting diode is presented
Phonon Modeling in Nano- and Micro- scale Crystalline Systems
Submicrometer phonon systems are becoming increasingly relevant in modern day technology. Phonon mechanisms are notably relevant in a number of solid-state devices including lasers, LEDs, transistors, and thermoelectrics. Proliferation of these devices has been driven by advancements in silicon-on-insulator technology. These advancements have allowed for the manufacture of devices with complex nanostructures and dimensions deep in the sub-microscale regime. However, accompanying improvements in the manufacture and design of novel crystalline systems is the requirement for accurate computational approaches for phonon modeling in nanostructured, anisotropic, and complex materials. The phonon Boltzmann transport equation is uniquely well suited to modeling energy transfer at the nano- and micro- meter length scales and is therefore an excellent candidate for this simulation task. However, current Boltzmann modeling approaches utilize a range of assumptions and simplifications that restrict their validity to isotropic, nominally one or two dimensional, or compositionally simple systems.
In this dissertation we present an original finite volume-based methodology for the solution of the three dimensional full Brillouin zone phonon Boltzmann transport equation. This methodology allows for separate real and reciprocal space discretization. By taking a sampling of vibrational modes throughout the first Brillouin zone our methodology captures three unique sources of phonon anisotropy. We investigate the effect of phonon anisotropy in a fin field effect transistor, calculating the effect that incorporating various sources of anisotropy has on the resultant temperature fields.
In a second study, we consider phonon flow through silicon nanowires with a modified boundary geometry. The three-dimensional flow fields are calculated and thermal transport below the Casimir limit is observed. Reduction in thermal conductivity is a result of maximizing the phonon backscatter that occurs in our phononic system. The backscatter serves to create regions of highly misaligned phonon flux. In addition, our silicon nanowire geometry has properties analogous with a high-pass phonon filter.
In the final study we apply our Boltzmann transport methodology to the simulation of phonon transport in the energetic material, RDX. We study phonon transport in the vicinity of a material hotspot, the location at which chemistry initiates in the material. By applying Boltzmann modeling, applied for the first time to this material, we gain valuable insights into the interplay between thermal transport and phonon modes linked with initiation
Simulation and Modeling of Nanomaterials
This Special Issue focuses on computational detailed studies (simulation, modeling, and calculations) of the structures, main properties, and peculiarities of the various nanomaterials (nanocrystals, nanoparticles, nanolayers, nanofibers, nanotubes, etc.) based on various elements, including organic and biological components, such as amino acids and peptides. For many practical applications in nanoelectronics., such materials as ferroelectrics and ferromagnetics, having switching parameters (polarization, magnetization), are highly requested, and simulation of dynamics and kinetics of their switching are a very important task. An important task for these studies is computer modeling and computational research of the properties on the various composites of the other nanostructures with polymeric ferroelectrics and with different graphene-like 2-dimensional structures. A wide range of contemporary computational methods and software are used in all these studies
Elucidating the Electronic Origins of Intermolecular Forces in Crystalline Solids
It is not possible to study almost any physical system without considering intermolecular forces (IMFs), no matter how insignificant they may appear relative to other energetic factors. Countless studies have shown that IMFs are responsible for governing a wide variety of physical properties, but often the atomic-origins of such interactions elude experimental detection. A considerable amount of work throughout the course of this research was therefore placed on using quantum mechanical simulations, specifically density functional theory (DFT), to calculate the electronic properties of solid-materials. The goal of these calculations was a better understanding of the precise origins of interatomic energies, down to the single-electron level. Furthermore, experimental X-ray diffraction and terahertz spectroscopy were both utilized because they are able to broadly probe the potential energy surfaces of molecular crystals, enhancing the theoretical data. Combining DFT calculations with experimental measurements enabled in-depth studies into the nature of specific non-covalent interactions, with results that were often unexpected based on conventional descriptions of IMFs. Overall, this work represents a significant advancement in understanding how subtle changes in characteristics like orbital occupation or electron density can have profound effects on bulk properties, highlighting the fragile relationship that exists between the numerous energetic parameters occurring within condensed phase systems
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