Chemistry Commons^™

Accelerated Broadband Spectra And Attosecond Charge Migration Simulations Using Real-Time Time-Dependent Density Functional Theory, Adam S. Bruner

LSU Doctoral Dissertations

In this dissertation, the calculations of light-matter interactions offer insight into the structure and dynamical response of electrons in molecular systems. Such information is useful for characterizing molecules, electronic structure, photochemistry, photomaterials, and a host of other applications. In the first part of this work, simulations of broadband absorption spectra are accelerated by the use of Pad´e approximanants of Fourier Transforms and dipole decomposition. Electronic absorption spectra from valence and core levels are obtained using time-dependent methods and compared to results from established perturbative techniques. In addition, core level absorption spectra are calculated for a nickel porphyrin and shown to …

The Spin-Forbidden A^4z-—X^2n(1/2) Transition Of Geh Detected In Absorption Using Intracavity Laser Spectroscopy, James O'Brien, L. O'Brien, L. Harms

Chemistry & Biochemistry Faculty Works

The a 4Σ--X 2Π1/2 transition of GeH has been recorded in absorption for the first time using Intracavity Laser Spectroscopy (ILS). The GeH molecules were produced in a 0.40-0.60 A DC plasma discharge inside an aluminum hollow cathode, using 500 mTorr of Ar, 100 mTorr of H2, and 200 mTorr of GeH4. This cathode is located within the resonator cavity of a Coherent Verdi™ V-10 pumped dye laser. Effective path lengths for this series of measurements using the ILS method ranged from 2 to 7 km. Spectra were calibrated using the absorption spectrum of I2 collected from an extracavity cell, …

Spectroscopy And Formation Of Lanthanum-Hydrocarbon Radicals Formed By Association And Carbon-Carbon Bond Cleavage Of Isoprene, Wenjin Cao, Dilkrushi Hewage, Dong-Sheng Yang

Chemistry Faculty Publications

La atom reaction with isoprene is carried out in a laser-vaporization molecular beam source. The reaction yields an adduct as the major product and C—C cleaved and dehydrogenated species as the minor ones. La(C₅H₈), La(C₂H₂), and La(C₃H₄) are characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of all three species exhibit a strong origin band and several weak vibronic bands corresponding to La-ligand stretch and ligand-based bend excitations. La(C₅H₈) is a five-membered metallacycle, whereas La(C₂H_{2 …}

Diagnostic Platform For Current Health Status Monitoring, Albert S. Benight, Megan M. Koslen, Matthew W. Eskew

Student Research Symposium

Our approach is based on physical measurements of blood plasma and exploits the plethora of information contained in the human plasma proteome, as a reporter of human health status. The assay involves collection and analysis ofthermograms of plasma from human blood measured by differential scanning calorimetry (DSC).

Plasma thermograms arise from the temperature-induced denaturation profile of proteins within blood plasma measured by DSC. This insightful measurement thereby provides a snapshot of the current state of the human plasma proteome which directly informs on overall systemic health. Such measurements have been shown to be highly accurate and sensitive indicators of health …

Surface Reaction And Diffusion Kinetics In Semiconducting Metal Oxide Film Gas Sensors, Aravind Reghu

Electronic Theses and Dissertations

Chemiresistive metal oxide gas sensors based on materials such as SnO₂, ZnO, and TiO₂, have been investigated extensively by many researchers for a wide range of applications. The band bending model, based on the surface chemistry of highly reactive ionosorbed species (O₂^- or O^-) and the semiconducting material properties of SnO₂, TiO₂ and ZnO, adequately predicts the dependence of the change in sensor conductivity (Δσ) as a function of target gas pressure and temperature. However, the band bending model is not applicable to gas sensors based on reducible oxides …

Developing Kenya’S Educational Capacity In Nuclear Security Through Nuclear Forensics Research, Hudson Kalambuka Angeyo

International Journal of Nuclear Security

Nuclear energy’s distinctive characteristics give rise to special educational requirements. These requirements are necessary to not only address the danger of nuclear proliferation, but also to build capacity for a secure nuclear fuel circle. In this paper, I assess the status of educational capacity in nuclear security both in response to, and in support of, Kenya’s nuclear power program. I highlight the nuclear security educational infrastructure’s key features in the context of nuclear power, noting the low capacity at Kenyan universities. I identify the steps required to ensure that the country’s dynamic nuclear regulatory infrastructural framework is used effectively to …

Compact Sensing Platforms Based On Localized Surface Plasmon Resonance, Zhutian Ding

Electronic Thesis and Dissertation Repository

The development of plasmonic sensors mainly focuses on the improvement of their sensitivities that are approaching the theoretical limit. This work aims to propose, fabricate and characterize compact sensing platforms that are highly adaptable and easy to be miniaturized, without compromising their sensitivities. A plasmonic sensing system that allows the excitation of localized surface plasmon resonance (LSPR) by individual waveguide modes is presented conceptually and experimentally. Another compact sensing platform is proposed based on the ensemble hypothesis developed in this thesis.

Variable Temperature Thermochromic Switching Under Varying Illumination, Alexis Corbett, Danielle Hall, John E. Sinko

Huskies Showcase

Award for "Runner-Up Poster Presentation".

Abstract

Minnesota is home to some of the greatest temperature ranges in the United States, with lows reaching below -40º Celsius and highs reaching nearly 40ºC. This results in higher than average spending on the heating and cooling of buildings. We have been investigating into responsive building materials to help address this. In particular, we have been studying a thermochromic paint that can capture solar energy and transfer it into the building as heat at low temperatures and reflect the energy at higher temperatures to keep the building cooler.

Time-Dependent Efficiency Measurements Of Polymer Solar Cells With Dye Additives: Unexpected Initial Increase Of Efficiency, Kyle J. Bandaccari, Grace E. Chesmore, Mitchel Bugaj, Parisa Tajalli-Tehrani Valverde, Richard P. Barber Jr., Brian J. Mcnelis

Physics

We report the effects of the addition of two azo-dye additives on the time-dependent efficiency of polymer solar cells. Although the maximum efficiencies of devices containing different amounts of dye do not vary greatly over the selected concentration range, the time dependence results reveal a surprising initial increase in efficiency in some samples. We observe this effect to be correlated with a leakage current, although a specific mechanism is not yet identified. We also present the measured lifetimes of these solar cells, and find that variations in dye concentrations produce a small effect at most. Characterization of the bulk heterojunction …

Characterization Of Polymers Containing Ferrocene And Imidazole With Density Functional Theory, Eric Mullins

Electronic Theses & Dissertations

Electrochemical and UV-Vis studies on these polymers in the presence of aqueous solutions containing metal ions have revealed significant modifications in the electrochemical properties and absorption spectra. These modifications in electrochemical properties could be attributed to the ability of the imidazole to coordinate with metal ions, increasing its electron deficiency and enhancing oxidization of the nearby ferrocene moiety if it is in close proximity with imidazole. However, the mechanism of interaction between the imidazole and metal ions, as well as the equilibrium geometry of the resulting polymer-metal ion complex is unknown.

In this thesis, density functional theory (DFT) was used …

Factors Affecting The Number And Type Of Student Research Products For Chemistry And Physics Students At Primarily Undergraduate Institutions: A Case Study., Birgit Mellis, Patricia Soto, Chrystal D. Bruce, Graciela Lacueva, Anne Wilson, Rasitha Jayasekare

2018 Faculty Bibliography

For undergraduate students, involvement in authentic research represents scholarship that is consistent with disciplinary quality standards and provides an integrative learning experience. In conjunction with performing research, the communication of the results via presentations or publications is a measure of the level of scientific engagement. The empirical study presented here uses generalized linear mixed models with hierarchical bootstrapping to examine the factors that impact the means of dissemination of undergraduate research results. Focusing on the research experiences in physics and chemistry of undergraduates at four Primarily Undergraduate Institutions (PUIs) from 2004–2013, statistical analysis indicates that the gender of the student …

Volume 10, Taylor Hogg, Tiffany Carter, Brandyn Johnson, Haleigh James, Josh Baker, Tyler Cernak, Kirsten Bauer, Allie Snavely, Mary Zell Galen, Eric Powell, Thomas Wise, Katie Kinsey, Beth Barbolla, Maeleigh Ferlet, Rebecca Morra, Michala Day, Alexandra Evangelista, Max Flores, Harley Hodges, Clardene Jones, Harrison Samaniego, Jamesha Watson, Abby Gargiulo, Heather Green, Haley Klepatzki, Juan Guevara, Dani Bondurant, Michael Joseph Link Jr., Pamela Dahl, Maeve Losen, Charlotte Murphey

Incite: The Journal of Undergraduate Scholarship

Introduction Dr. Roger A. Byrne

An Analysis of Media Framing in Cases of Violence Against Women by Taylor Hogg

Writing in the Discipline of Nursing by Tiffany Carter

Photography by Brandyn Johnson

The Hidden Life of Beef Cattle: A Study of Cattle Welfare on Traditional Ranches and Industrial Farms by Haleigh James

Bloodworth's by Josh Baker and Tyler Cernak

Prosimians: Little Bodies, Big Significance by Kirsten Bauer

Skinformed by Allie Snavely

Coopertition and Gracious Professionalism: The Effects of First Robotics Folklore and Culture on the Stem Community by Mary Zell Galen

Tilt by Eric Powell And Thomas Wise

The Millennial …

Nadph-Cytochrome P450 Oxidoreductase: Extraction Of The Full-Length Protein And Methyl-Trosy Nmr Of The Soluble Mutants, Sara Ali Jamal Arafeh

Master's Theses (2009 -)

NADPH-cytochrome p450 oxidoreductase (CYPOR) is a membrane-bound protein in living cells. CYPOR delivers electrons to cytochrome p450 proteins (CYPs) to catalyze metabolism of drugs and synthesis of steroids. Extraction and solubilization of CYPOR from the membrane is typically done with the TritonX-100 detergent. The amount of the solubilized protein by this detergent, however, remains relatively low to structurally analyze CYPOR with NMR spectroscopy. The goal of the first project in this thesis was to optimize the amount of the extracted CYPOR from the E. coli membrane using various detergents and additives. To this aim, non-ionic detergents with variable hydrophobicity (TritonX-100, …

Hyperpolarization Of Silicon Nanoparticles With Tempo Radicals, Jingzhe Hu, Nicholas Whiting, Pratip Bhattacharya

Nicholas Whiting

Functionalized Nanoporous Carbon Scaffolds For Hydrogen Storage Applications, Christopher Carr

Dissertations

Recent efforts have demonstrated confinement in porous scaffolds at the nanoscale can alter the hydrogen sorption properties of metal hydrides, though not to an extent feasible for use in onboard hydrogen storage applications, proposing the need for a method allowing further modifications. The work presented here explores how the functionalization of nanoporous carbon scaffold surfaces with heteroatoms can modify the hydrogen sorption properties of confined metal hydrides in relation to non-functionalized scaffolds (FS). Investigations of nanoconfined LiBH₄and NaAlH₄indicate functionalizing the carbon scaffold surface with nitrogen can shift the activation energy of hydrogen desorption in excess of …

Improving Fallout Characterization By Using Multivariate Techniques To Determine Composition, Christopher R. Pitkins

Theses and Dissertations

Multivariate statistical techniques have been applied in order to un-mix nuclear fallout debris chemical data. This information is critical to characterization of fallout particle formation following a nuclear detonation. Understanding the correlation between environmental precursors and actinide concentrations in post-detonation nuclear fallout material aids in understanding the physical and chemical processes that alter nuclear device signatures in the fireball. This research examines 123 nuclear fallout samples from a historical nuclear test. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) are used to collect chemical compositions of the fallout samples. Principal component analysis (PCA) is applied in order to examine …

Investigation Of Temperature Response Of Photopolymer Material Used For Holographic Sensor, Muhammad Irfan, Tatsiana Mikulchyk, Suzanne Martin, Izabela Naydenova

Conference Papers

Recently, functionalised photopolymer has emerged as a versatile recording material in the field of optical holography due to its novel characteristics and potential use in the development of holographic based sensors, and optical elements. This work describes the temperature response of a newly developed photopolymer, containing of a monomer Nisopropylacrylamide (NIPA) which under photopolymerisation forms a temperature sensitive polymer - Poly(Nisopropylacrylamide) (PNIPA). The photonic sensor was developed by holographic recording of volume phase transmission gratings in a self-processing NIPA-based polymer with a 532 nm laser beam. A 633 nm probe beam was used to monitor real time diffraction efficiency (DE) …

The "Double Standard" Of Nonproliferation: Regime Type And The U.S. Response To Nuclear Weapons Program, Alina Shymanska

International Journal of Nuclear Security

There is no doubt that the NPT regime is far from being equal for all states involved. As the predominant hegemonic power since WWII, the United States plays a major role in deciding the fates of non-great power proliferators. This article tries to find the logical explanation of the phenomenon whereby some nuclear proliferators are absolved regardless of their active accumulation of nuclear arsenals while others are labeled as “rogue states” and ordered to disarm. The article suggests that a particular proliferator’s political regime could affect the way in which its state is approached by the U.S., known for its …

Investigation Of Novel Electrolytes For Use In Lithium-Ion Batteries And Direct Methanol Fuel Cells, Kartik Pilar

Dissertations, Theses, and Capstone Projects

Energy storage and conversion plays a critical role in the efficient use of available energy and is crucial for the utilization of renewable energy sources. To achieve maximum efficiency of renewable energy sources, improvements to energy storage materials must be developed. In this work, novel electrolytes for secondary batteries and fuel cells have been studied using nuclear magnetic resonance and high pressure x-ray scattering techniques to form a better understanding of dynamic and structural properties of these materials. Ionic liquids have been studied due to their potential as a safer alternative to organic solvent-based electrolytes in lithium-ion batteries and composite …

Lanthanum-Mediated Dehydrogenation Of Butenes: Spectroscopy And Formation Of La(C4H6) Isomers, Wenjin Cao, Dilkrushi Hewage, Dong-Sheng Yang

Chemistry Faculty Publications

La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(C₄H₆) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(C₄H₆) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these …

Detection And Characterization Of The Tin Dihydride (Snh2 And Snd2) Molecule In The Gas Phase, Tony C. Smith, Dennis J. Clouthier

Chemistry Faculty Publications

The SnH₂ and SnD₂ molecules have been detected for the first time in the gas phase by laser-induced fluorescence (LIF) and emission spectroscopic techniques through the ùB₁–X̃¹A₁ electronic transition. These reactive species were prepared in a pulsed electric discharge jet using (CH₃)₄Sn or SnH₄/SnD₄ precursors diluted in high pressure argon. Transitions to the electronic excited state of the jet-cooled molecules were probed with LIF, and the ground state energy levels were measured from single rovibronic level emission spectra. The LIF spectrum of SnD_{2 …}

Hyperuniformity With No Fine Tuning In Sheared Sedimenting Suspensions, Joseph Paulsen, J. M. Schwarz, Jikai Wang

Physics - All Scholarship

Particle suspensions, present in many natural and industrial settings, typically contain aggregates or other microstructures that can complicate macroscopic flow behaviors and damage processing equipment. Recent work found that applying uniform periodic shear near a critical transition can reduce fluctuations in the particle concentration across all length scales, leading to a hyperuniform state. However, this strategy for homogenization requires fine tuning of the strain amplitude. Here we show that in a model of sedimenting particles under periodic shear, there is a well-defined regime at low sedimentation speed where hyperuniform scaling automatically occurs. Our simulations and theoretical arguments show that the …

Mc-Pdft Can Calculate Singlet-Triplet Splittings Of Organic Diradicals., Samuel J. Stoneburner, Donald G. Truhlar, Laura Gagliardi

Educator Scholarship

The singlet-triplet splittings of a set of diradical organic molecules are calculated using multiconfiguration pair-density functional theory (MC-PDFT) and the results are compared with those obtained by Kohn-Sham density functional theory (KS-DFT) and complete active space second-order perturbation theory (CASPT2) calculations. We found that MC-PDFT, even with small and systematically defined active spaces, is competitive in accuracy with CASPT2, and it yields results with greater accuracy and precision than Kohn-Sham DFT with the same parent functional. MC-PDFT also avoids the challenges associated with spin contamination in KS-DFT. It is also shown that MC-PDFT is much less computationally expensive than CASPT2 …

X-Ray Spectroscopy Of Nio And Nanodiamond At Ssrl, Jackson Earl

STAR Program Research Presentations

The first aspect of this research project focuses on investigating the surface chemistry of high pressure high temperature (HPHT) nanodiamond by using X-ray spectroscopy techniques at the Stanford Synchrotron Radiation Lightsource (SSRL). HPHT nanodiamond is being examined as a biosensing tool for electric field detection based on the fluorescent nitrogen vacancy center hosted within diamond. With use of the transition edge spectrometer (TES), a state-of-the-art X-ray fluorescence detector, we are able to probe the surface and bulk properties of diamond. Preliminary work using density functional theory (DFT) has been done, offering insight into ground state energies and electronic structure. DFT …

Tunable Surface Interactions In Adsorbing Polymer Solutions, Sorour Hosseini

Open Access Theses & Dissertations

A simple formalism is suggested, to calculate the most likely configuration of a finite polymer, between two surfaces on which the monomers can adsorb. Grafted polymers typically enhance the stability of colloidal dispersions, via the long ranged steric repulsion due to the overlap of their polymer brushes, which can be thicker that the typical range of the DLVO interactions. However, if the polymers are adsorbing on the colloidal surfaces, there is the possibility of bridge formation between particles and therefore long-range attractions are induced (a procedure commonly used for the flocculation of colloidal suspensions). The two effects are competing and …

Robust, Bridge-Less Ion-Selective Electrodes With Significantly Reduced Need For Pre- And Post-Application Handling, Benjamin Schazmann, S. Demey, Z. Waqar Ali, M-S Plissart, E. Brennan, A. Radu

Articles

We are demonstrating robust, single-layer ion-selective electrode (ISE) utilizing simple Ag/AgCl electrode as solid support without the need for intermediate polymer layer. We have created and chemically linked a family of imidazolium ionic liquids (ILs) with poly (vinyl chloride) (PVC) using click chemistry, resulting in hybrid materials with tunable characteristics. The resultant material inherently contains chloride ion thus offering the ability to stabilize interfacial potential. This allowed us to construct very simple, single-layer membranes with significantly reduced need for conditioning as an added bonus compared to traditional sensors. Chemical immobilization of ISE membrane components also led to extended lifetime as …

Analysis Of The Red And Green Optical Absorption Spectrum Of Gas Phase Ammonia, Nikolai F. Zobov, Phillip A. Coles, Roman I. Ovsyannikov, Aleksandra A. Kyuberis, Robert J. Hargreaves, Peter F. Bernath, Jonathan Tennyson, Sergei N. Yurchenko, Oleg L. Polyansky

Chemistry & Biochemistry Faculty Publications

Room temperature NH₃ absorption spectra recorded at the Kitt Peak National Solar Observatory in 1980 are analyzed. The spectra cover two regions in the visible: 15,200 - 15,700 cm^-1 and 17,950 - 18,250 cm^-1. These high overtone rotation-vibration spectra are analyzed using both combination differences and variational line lists. Two variational line lists were computed using the TROVE nuclear motion program: one is based on an ab initio potential energy surface (PES) while the other used a semi-empirical PES. Ab initio dipole moment surfaces are used in both cases. 95 energy levels with J = 1 …

Plasmon-Enhanced Optical Sensing By Engineering Metallic Nanostructures, Peng Zheng

Graduate Theses, Dissertations, and Problem Reports

The world’s booming population projected to reach 10 billion by 2050 causes enormous stresses on environmental safety, food supply, and healthcare, which in return threatens human civilizations. One of the most promising solutions lies at innovating point-of-care (POC) sensing technologies to conduct detection of environmental hazards, monitoring of food safety, and early diagnosis of diseases in a timely and accurate manner. The discovery of surface-enhanced spectroscopy in the 1970s has significantly stimulated research on light-matter interaction which gives rise to enhanced optical phenomena such as surface-enhanced Raman scattering (SERS), plasmon-enhanced fluorescence (PEF), and particularly, they have found enormous applications in …

Single-Site Catalyst Promoters Accelerate Metal- Catalyzed Nitroarene Hydrogenation, Liang Wang, Erjia Guan, Jian Zhang, Junhao Yang, Yihan Zhu, Yu Han, Ming Yang, Cheng Cen, Gang Fu, Bruce C. Gates, Feng-Shou Xiao

Faculty & Staff Scholarship

Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydro- genation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn- TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various …

Block-Copolymer Assisted Fabrication Of Anisotropic Plasmonic Nanostructures, Calbi J. Gunder

MSU Graduate Theses

The anisotropic nanostructures of noble metals are of great interest for plasmonic applications due to the possibility of tuning the localized surface plasmon resonance (LSPR) across the UV-VIS-NIR without sacrificing the linewidth as well as to achieve larger local field enhancement. Here, we report a simple and promising fabrication method of anisotropic gold nanostructures film using polystyrene-b-2vinylpyridine (PS-b-P2VP) block copolymers (BCP) as a template. In this approach, PS-b-P2VP spherical micelles were first synthesized as a template followed by selective deposition of Au precursor inside P2VP core of the micelles using ethanol solution of Au salt. Subsequently, heat treatment of the …