Physical Chemistry Commons^™

Ultrafast Rempi In Benzene And The Monohalobenzenes Without The Focal Volume Effect, Timothy D. Scarborough, James Strohaber, David B. Foote, Collin J. Mcacy, Cornelis J. Uiterwaal

C.J.G.J. Uiterwaal Publications

We report on the photoionization and photofragmentation of benzene (C₆H₆) and of the monohalobenzenes C₆H₅–X (X = F, Cl, Br, I) under intense-field, single-molecule conditions. We focus 50-fs, 804-nm pulses from a Ti:sapphire laser source, and record ion mass spectra as a function of intensity in the range ~10¹³ W/cm² to ~10¹⁵ W/cm². We count ions that were created in the central, most intense part of the focal area; ions from other regions are rejected. For all targets, stable parent ions (C₆H₅X+) are …

Electronic Structure Characterization Of Nanocrystalline Surfaces And Interfaces With Photoemission Spectroscopy, Sebastian Gutmann

USF Tampa Graduate Theses and Dissertations

In this study, photoemission spectroscopy (PES) was used to investigate the electronic properties of nanocrystalline titanium dioxide (TiO₂), zinc oxide (ZnO), and cadmium selenide (CdSe). Electrospray deposition technique enabled the preparation of thin films in vacuum from a dispersion prepared outside the vacuum chamber. This method also allowed the step-wise formation of interfaces and the monitoring of the evolution of the electronic structure with intermittent PES characterization.

The work function of nanocrystalline TiO₂ and ZnO was measured with ultraviolet photoemission spectroscopy (UPS) and low-intensity x-ray photoemission spectroscopy (LIXPS). Measurements on environmentally contaminated surfaces revealed an instantaneous and …

Elastic Properties Of Poly(Vinyldene Fluoride) (Pvdf) Crystals: A Density Functional Theory Study, Yong Pei, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We computed structural and elastic properties of totally nine phases of poly(vinyldene fluoride) (PVDF) crystals using the density-functional theory (DFT) method with and without inclusion of the dispersion corrections. In addition to the four known crystalline forms, mechanic properties of five theoretically predicted crystalline forms of PVDF are also investigated. The all-trans form I_p exhibits the largest cohesive energy, bulk, and Young’s modulus among the nine crystalline forms. The DFT calculations suggest that the δ crystalline forms (III_au, III_pu, III_pd, and III_ad) possess poor chain rigidity among the nine PVDF …

Structure Evolution Of Gold Cluster Anions Between The Planar And Cage Structures By Isoelectronic Substitution: AuN− (N = 13–15) And MauN− (N = 12–14; M = Ag, Cu), Rhitankar Pal, Lei-Ming Wang, Wei Huang, Lai-Sheng Wang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

The structural and electronic effects of isoelectronic substitution by Ag and Cu atoms on gold cluster anions in the size range between 13 and 15 atoms are studied using a combination of photoelectron spectroscopy and first-principles density functional calculations. The most stable structures of the doped clusters are compared with those of the undoped Au clusters in the same size range. The joint experimental and theoretical study reveals a new C_3v symmetric isomer for Au₁₃ ⁻, which is present in the experiment, but has hitherto not been recognized. The global minima of Au₁₄ ⁻ and Au …

Nonuniformity In Lattice Contraction Of Bismuth Nanoclusters Heated Near Its Melting Point, A. Esmail, M. Abdel-Fattah, Hani E. Elsayed-Ali

Electrical & Computer Engineering Faculty Publications

The structural properties of bismuth nanoclusters were investigated with transmission high-energy electron diffraction from room temperature up to 525 ± 6 K. The Bi nanoclusters were fabricated by thermal evaporation at room temperature on transmission electron microscope grids coated with an ultrathin carbon film, followed by thermal and femtosecond laser annealing. The annealed sample had an average cluster size of ∼14 nm along the minor axis and ∼16 nm along the major axis. The Debye temperature of the annealed nanoclusters was found to be 53 ± 6 K along the [012] direction and 86 ± 9 K along the [110] …

Theoretical Characterization Of Non-Covalent Weakly Bound Clusters Through The Application Of Sophisticated Computational Quantum Chemistry Methodologies And The Development Of Integrated Fragmentation Techniques, Desiree Bates

Electronic Theses and Dissertations

Non-covalent, weakly bound clusters have been and remain of significant interest to many researchers. However, with computational studies, accurate description of these interactions requires sophisticated electronic structure methods employing large basis sets. This methodology becomes extremely computationally demanding as the size of the system increases. This work presents benchmark data and explores methods for obtaining highly accurate ab initio results for larger systems at greatly reduced computational costs. CCSD(T) complete basis set limit interaction energies are presented for a variety of parallel-slipped π...π dimers and low-lying isomers of (h₂o)₆. The calibration of a 2-body:Many-body fragmentation method …

Precise Control Of Highly Ordered Arrays Of Nested Semiconductor/Metal Nanotubes, Diefeng Gu, Helmut Baumgart, Kandabara Tapily, Pragya Shrestha, Gon Namkoong, Xianyu Ao, Frank Müller

Electrical & Computer Engineering Faculty Publications

Lithographically defined microporous templates in conjunction with the atomic layer deposition (ALD) technique enable remarkable control of complex novel nested nanotube structures. So far three-dimensional control of physical process parameters has not been fully realized with high precision resolution, and requires optimization in order to achieve a wider range of potential applications. Furthermore, the combination of composite insulating oxide layers alternating with semiconducting layers and metals can provide various types of novel applications and eventually provide unique and advanced levels of multifunctional nanoscale devices. Semiconducting TiO₂ nanotubes have potential applications in photovoltaic devices. The combination of nanostructured semiconducting materials …

Evaluation Of The Physicochemical Properties And Stability Of Solid Lipid Nanoparticles Designed For The Delivery Of Dexamethasone To Tumors, Melissa Howard

University of Kentucky Doctoral Dissertations

Pre-clinical and clinical trials suggest that pre-treatment with dexamethasone (Dex) may facilitate enhanced uptake of subsequently administered chemotherapeutic agents. To reduce the side effects associated with systemic administration of Dex, solid lipid nanoparticles (SLNs) containing dexamethasone palmitate (Dex-P) were prepared as a means of achieving tumor-targeted drug delivery. These studies were aimed at evaluating the physicochemical properties and both the physiological and storage stability of the SLNs.

SLNs were prepared using nanotemplate engineering technology. Stearyl alcohol (SA) was used as the lipid phase with Brij^® 78 and Polysorbate 60 as surfactants and PEG6000 monostearate as a long-chain PEGylating agent. …

Band Structures Of Layered Carbon/Boron Nitride Materials With Commensurate Lattices, Christopher C. Wells

Legacy Theses & Dissertations (2009 - 2024)

The electronic structures of systems consisting of hexagonal boron nitride layers and graphite sheets have been investigated in detail using density functional theory methods with two exchange correlation functions (local density approximation and generalized gradient approximation). The experimental data of graphene, graphite, monolayer hexagonal BN, and hexagonal BN were reproduced well with computational models. The commensurate models used in the investigation were generated by taking the averages of the lattice constants for graphite and h-BN.

Investigation Of Titanium Nitride As Catalyst Support Material And Development Of Durable Electrocatalysts For Proton Exchange Membrane Fuel Cells, Bharat Avasarala

Legacy Theses & Dissertations (2009 - 2024)

The impending energy and climatic crisis makes it imperative for human society to seek non-fossil based alternative sources for our energy needs. Although many alternative energy technologies are currently being developed, fuel cell technology provides energy solutions, which satisfy a wide range of applications. But the current fuel cell technology is far from its target of large scale commercialization mainly because of its high cost and poor durability. Considerable work has been done in reducing the cost but its durability still needs significant improvement. Of the various materials in a PEM fuel cell, the degradation of electrocatalyst affects its durability …

Dynamic Light Scattering And Zeta Potential Of Colloidal Mixtures Of Amelogenin And Hydroxyapatite In Calcium And Phosphate Rich Ionic Milieus, Vuk Uskoković, Roselyn Odsinada, Sonia Djordjevic, Stefan Habelitz

Pharmacy Faculty Articles and Research

The concept of zeta-potential has been used for more than a century as a basic parameter in controlling the stability of colloidal suspensions, irrespective of the nature of their particulate ingredients – organic or inorganic. There are prospects that self-assembly of peptide species and the protein-mineral interactions related to biomineralization may be controlled using this fundamental physicochemical parameter. In this study, we have analyzed the particle size and zeta-potential of the full-length recombinant human amelogenin (rH174), the main protein of the developing enamel matrix, in the presence of calcium and phosphate ions and hydroxyapatite (HAP) particles. As calcium and phosphate …

Fourier Transform Emission Spectroscopy Of Yh And Yd: Observation Of New A¹Δ And B¹Π Electronic States, R. S. Ram, G. Li, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

The emission spectra of YH and YD molecules have been investigated in the 3600–12 000 cm⁻¹ region using a Fourier transform spectrometer. Molecules were formed in an yttrium hollow cathode lamp operated with a continuous flow of a mixture of Ne and Ar gases, and YH and YD were observed together in the same spectra. A group of bands observed near 1 μm have been identified as 0-0 and 1-1 bands of the A¹Δ-X¹Σ⁺ and B¹Π-X¹Σ⁺ transitions of YH and the 0-0 bands of the same two transitions …

Density Functional Calculation Of The Structure And Electronic Properties Of CuNON (N = 1−8) Clusters, Gyun-Tack Bae, Randall W. Hall, Barry Dellinger

Randall W. Hall

Ftir And Diode Laser Spectroscopy Of Isobutylene.Pdf, Trocia N. Clasp, Scott Reeve

Scott Reeve

No abstract provided.

Chemical And Electronic Structure Of Surfaces And Interfaces In Compound Semiconductors, Sujitra Pookpanratana

UNLV Theses, Dissertations, Professional Papers, and Capstones

The interface formation between two different materials is important in applications for optoelectronic devices. Often, the success or performance of these devices is dependent on the formation of these heterojunctions. In this work, the surface and interfaces in such materials for optoelectronic devices are investigated by a suite of X-ray analytical techniques including X-ray photoelectron (XPS), X-ray excited Auger electron (XAES), and X-ray emission (XES) spectroscopies to provide novel insight.

For the group III-nitrides (e.g., AlxGa1-xN) used in many light emitting devices, a significant challenge exists to form an Ohmic contact. The electron affinities and band gaps of GaN and …

Ab Initio Search For Novel Bxhy Building Blocks With Potential For Hydrogen Storage, Jared K. Olson

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

On-board hydrogen storage presents a challenging barrier to the use of hydrogen as an energy source because the performance of current storage materials falls short of platform requirements. Because boron is one of the lightest chemical elements that can form strong covalent bonds with hydrogen, it provides an excellent opportunity to design new lightweight materials on the basis of novel boron hydride building blocks. Realizing this potential requires an understanding of the electronic structure, chemical bonding, and stability of neutral and anionic B_xH_y clusters with variable stoichiometry. While a large number of boron hydride compounds are known, …

Synthesis And Catalytic Activity Of Nanostructured Cerium Oxide, Neil J. Lawrence

Department of Chemistry: Dissertations, Theses, and Student Research

Cerium oxide (ceria, CeO_2-x where x is 0 to 0.5) has been one of the most widely used heterogeneous catalysts particularly in three way catalytic converters. Most of the catalytic traits can be attributed to two properties of ceria: first, the high mobility and storage capacity of oxygen within the lattice; second, the ease with which cerium changes between Ce³⁺ and Ce⁴⁺ states. These properties, combined with the abundance of cerium on earth, make ceria a low-cost highly effective alternative to noble metal catalysts. Recent research has been focused on the nanoscale properties of ceria.

The effect …

Characteristics And Stability Of Oxide Films On Plutonium Surfaces, Harry Guillermo García Flores

Department of Chemistry: Dissertations, Theses, and Student Research

The oxidation of plutonium (Pu) metal continues to be an area of considerable activity. The reaction characteristics have significant implications for production use, storage, and disposition of this radiological material. Developing an accurate physical model of the structures, oxidation states, and oxygen concentration gradients present during oxidation are essential to understanding this process. Traditionally, the stable oxides of Pu have been thought to be plutonium sesquioxide (Pu₂O₃, O/Pu = 1.5, Pu³⁺) and plutonium dioxide (PuO₂, O/Pu = 2.0, Pu⁴⁺), existing in a layered structure on Pu metal. Many of the …

The Roles Of The Width Of Gas/Liquid/Solid Three-Phase Boundary Zone Of Dispersion Water Films In Atmospheric Corrosion Of Metals, Wang Jia, Jing Jiang

Journal of Electrochemistry

The roles of TPB(Three-Phase Boundary) width in the corrosion processes of metals under dispersed water films were investigated by electrochemical techniques combined with contact angle measurement.It is found that both cathodic limiting current density and corrosion current density linearly increases with increasing the TPB width,confirming the important role of TPB width in gas/liquid/solid multiphase corrosion systems.Based on above results,the effect of water film thickness on atmospheric corrosion rate was quantitatively evaluated by the TPB width.

Research On Nafion/Sio_2 Composite Membrane In All Vanadium Redox Flow Battery, Dong-Dong Liu, Mao-Cai Lin, Tao Guan, Qing-Chun Yu

Journal of Electrochemistry

The Nafion117/SiO2 composite membrane was prepared by sol-gel method.The results showed that,during composite membrane preparation process,the ratio of MeOH and TEOS did not affect the penetration rate of VO2+ basically,however,the lowest permeability of 427×10-9cm2/s in the membrane was achieved while hydrolysis time was 10 min and natural drying for 24 h after hydrolysis,which reduced by 52 times than that in Nafion117 membrane.The SEM tests proved that SiO2 grains grew bigger in the composite membrane during the natural drying,and most of the holes in Nafion117 were filled.Single cell test showed the battery power efficiency was improved by 2.7 %.

Electroless Deposition And Characterization Of Nickel Coating In Lead-And Cadmium-Free Bath, Fang-Zu Yang, Ming-Hui Chen, Xia-Jing Huang, Zhong-Qun Tian, Shao-Min Zhou

Journal of Electrochemistry

Technology of electroless nickel deposition in lead-and cadmium-free bath was developed.Coating′s morphology,composition,structure and electrochemical activity were characterized by SEM,EDS,XRD and electrochemical methods.The results showed that,the deposition rate of nickel in self-catalysing was 22.4 μm·h-1,which was increased by the increase of bath temperature and pH value.The effect of sodium hypophosphite on deposition rate was much more remarkable compared with nickel sulfate.The obtained nickel coating was 7.8% in phosphor weight content,having compact and neat surface morphology,amorphous structure,and good electrochemical corrosion resistance in sodium chloride solution.

Electrodeposition Of Lead Dioxide From Dluoroborate Solutions, Chun-Mei Kong, Yong-Ming Tang, Wen-Zhong Yang, Xiao-Yuan Yang

Journal of Electrochemistry

The PbO2 anodes were prepared on platinum from fluoroborate media and its doped solutions by electrodeposition technique.Elecchemical and pysicochemical properties of these PbO2 films were studied by cyclic voltammetry methods,XRD and SEM.The results showed that the presence of BF4-increased PbO2 electrodeposition rate;the prepared lead dioxide consisted of β-PbO2;the preferential orientation of crystals and surface morphology were affected a lot by doping F-and Fe3+.The FB/F-Fe-PbO2 electrode exhibited regular-shaped layers with compact morphology.Furthermore,increasing current density also change the preferential orientation of PbO2 crystals.

Electrochemical Performance Of Zinc Tetra (Trifluoroethoxy) Phthalocyaninate In Aqueous And Nonaqueous Solvents, Xiao-Shan Wu, Li-Ying Huang, Jin-Que Zhang, Shan-Lan Zhu

Journal of Electrochemistry

The cyclic voltammetric performance of ZnPcF in N,N-dimethylformaide(DMF),dimethyl sulfoxide(DMSO) solution and phosphate buffer solutions(PBS) has been examined.The results showed that four pairs of redox peaks appeared in nonaqueous solvents,and the values of half-wave redox potential were 0.558 V,-0.761 V,-1.034 V,-1.417 V,respectively,exhibiting four quasi-reversible phthalocyanine ligand based one-electron transfers.In PBS only two redox peaks were observed and the values of half-wave redox potential were-0.885 V,-1.104 V,exhibiting irreversible behavior characteristics.Comparing to the zinc phthalocyanine(unsubstitute ZnPc),introducing electron-withdrawing groups-trifluoroethoxyl to the peripheral sites of the phthalocyanines shifts the redox processes of the complex toward positive potentials.

Eis Study On The Change Of Resistance And Water Absorption During The Failure Graduation Of Inorganic Zinc-Rich/Epoxy/Aliphatic Polyurethane Composite Coatings, Shao-Ping He, Jin-Ping Xiong, Yu-Ming Tang, Yu Zuo

Journal of Electrochemistry

The failure process of inorganic zinc-rich/micaceous iron oxide epoxy/aliphatic polyurethane composite coatings in 3.5% NaCl solution under ultraviolet radiation(UV) was studied with Electrochemical Impedance Spectroscopy(EIS).The result shows that the protective property of the coating was enhanced with the increase of total coating thickness,but the degree of improvement reduced gradully as the coating thickness increased.The shielding effect of the micaceous iron oxide epoxy was mainly reflected in the initial period of the service process,while in later period the coating performance largely depended on the zinc-rich primer.The change of the water uptake in the composite coating presented a 'three-stage' characteristic.The thinner the …

Effects Of Solvents And Electrolyte Salts On The Electrochemical Reduction Of Oxygen In Non-Aqueous Electrolytes, Yan-Yan Tian, Wei Wu, Jun Gao, Yong Yang

Journal of Electrochemistry

The electrochemical reduction processes of oxygen in different non-aqueous solvents such as acetonitrile(MeCN),propylene carbonate(PC) and their mixtures were investigated by cyclic voltammetry method.The results indicated a one electron reduction of oxygen to O2-occured in these systems as a first step reduction,no matter whether in tetrabutylammonium hexafluorophosphate(TBAPF6)/MeCN or TBAPF6/PC electrolyte.However,the CV curves in 0.1 mol·L-1 TBAPF6/MeCN showed a couple of reversible redox peaks,indicating that the reduction process of oxygen was irreversible in the 0.1 mol·L-1 TBAPF6/PC electrolyte.In the PC-based electrolyte,the reduction current peak reduced largely and the oxidation peak of O2-almost disappeared as compared to that of the former electrolytes.The possible …

Electrochemical Detection For The Corrosion Of Reinforcing Steel In Concrete During Immersion And Drying Cycles, Bing-Li Jia, Fa-He Cao, An-Na Chen, Jian-Qing Zhang

Journal of Electrochemistry

The corrosion behavior of reinforcing steel in concrete under dry-wet cycle condition has been studied by electrochemical noise(EN) compared with the electrochemical impedance spectroscopy(EIS),SEM micrographs and EDS.The statistical method has been employed to analyze the EN data of reinforcing steel in concrete,which revealed three different corrosion stages of reinforcing steel in concrete,including the dissolution of the passive film,the active corrosion and the cumulation of corrosion product.The wavelet transform has also been employed,which indicated that steel in concrete with pH 1 is associated with uniform corrosion,while steel in concrete with pH 3 and pH 7 are associated with localized corrosion,such as …

Study Of The 11-Ferrocenylalkanethiol Redox-Induced Structure Changes By Flow-Injection Electrochemical Surface Plasmon Resonance, Xiu-Juan Xiao, Yong-Hui He, Juan Xiang, Bin Ren

Journal of Electrochemistry

Redox-induced orientation changes of self-assembled monolayers(SAMs) of 11-ferrocenylundecanethiol(FcC11SH) were studied by the flow-injection electrochemical surface plasmon resonance(FI-EC-SPR).Results indicated that there existed two mechanisms concerning the redox-induced structure change of the self-assembled monolayer of ferrocenylalkanethiols:the electrostatic repulsion between the positively charged surface and the ferricenium cation and that among the cations led to a decrease in the tilt angle of the alkanethiol chain;upon Fc oxidation,the Fc group rotated from a tilted conformation to a position where the cyclpentyldiene plane became perpendicular to the electrode.

Study On Aluminum Foils For Aluminum Electrolytic Capacitor, Hui-Zhong Tan, Guo-Qing Qian, Wen-Bao Wang, Lan Sun, Chang-Jian Lin

Journal of Electrochemistry

Scanning electron microscopy(SEM),X-ray diffraction(XRD),weight-loss method and electrochemical testing method were employed to study the chemical compositions and corrosion behaviors of hard foil and soft foil.The results showed that the surface morphology,chemical composition and crystal structure of hard foil and soft foil are different.It is found from electrochemical tests that the soft foil is suitable to the corrosion under low acidity conditions,which provides the base for developing the corrosion techniques under low acidity conditions.

Comparative Studies On The Deterioration Process Of Organic Coatings Under Immersed And Cyclic Wet-Dry Conditions By Eis, Yu-Nan Li, Jia Wang, Wei Zhang

Journal of Electrochemistry

Under the immersed and wet-dry cyclic conditions,the deterioration processes of the organic coatings on carbon steel surface have been comparatively studied by using electrochemical techniques.The wet-dry cycles were carried out in the alternating conditions of 12 h by immersing in a 3.5% sodium chloride solution and drying at 25 ℃ and 50% RH.Coating resistance,Rf,coating capacitance,Cf,and double layer capacitance,Cd,were monitored continuously and separately under above two conditions.The percentages of the intenfacial active area,Aw,were estimated from the obtained double layer capacitance,Cd.According to the EIS characteristics,the entire deterioration processes under above two mentioned conditions can be divided into three main stages,consisting of the …

Electrochemical Behaviors Of Organic Coating/Matal Substrate Under Simulated Deep Sea Environment Partⅰ.Effects Of Seawater Pressure On Transportation Behavior Of Water Through Coating And Coating′S Protective Performance, Bin Liu, Zhi-Gang Fang, Tao Wang, Hong-Bin Wang

Journal of Electrochemistry

By means of electrochemical impedance spectroscopy(EIS),the electrochemical behaviors of organic coating/metal substrate were studied under simulated deep sea environment in the laboratory.Effects of seawater pressure on the transportation behavior of water through coating and the protective performance of coating were analyzed.The experimental results showed that,compared to normal pressured seawater,there were different impedance characteristics of coating in 3.5 MPa pressured seawater.The main observations were that high seawater pressure accelerated the process of water uptake and invalidation of coating,increased water absorption,and lowered the anti-corrosion property of coating.