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Articles 91 - 120 of 121
Full-Text Articles in Chemistry
Speciation Behavior Of Americium Higher Oxidation States For The Separation Of Americium From Curium, Catherine Lynn Riddle
Speciation Behavior Of Americium Higher Oxidation States For The Separation Of Americium From Curium, Catherine Lynn Riddle
UNLV Theses, Dissertations, Professional Papers, and Capstones
Several countries are currently expanding the use of nuclear energy as a method for the safe generation of carbon free energy and a number are evaluating starting up a nuclear power program. Closed fuel cycle technologies may be key to waste reduction and a sustainable nuclear energy future and to support the development of more efficient fuel cycles, the investigation of the chemical properties of key actinides is at the forefront of separations research. In this work the characterization of higher oxidation states of americium (Am) has been performed using spectroscopic methods. Americium in the formal oxidation state of Am(V) …
A Combined First Principles Tddft And Experimental Study On The Uv-Vis Spectra Properties Of M(P-Nitrophenyl Azo Resorcinol)_3 Complexes (M: Fe, Cr), Tuğba Ari̇fi̇oğlu, Meli̇s Efeçinar, Nuray Şatiroğlu
A Combined First Principles Tddft And Experimental Study On The Uv-Vis Spectra Properties Of M(P-Nitrophenyl Azo Resorcinol)_3 Complexes (M: Fe, Cr), Tuğba Ari̇fi̇oğlu, Meli̇s Efeçinar, Nuray Şatiroğlu
Turkish Journal of Chemistry
UV-Vis absorption data of p-nitrophenyl azo resorcinol (Magneson I) and its 2 Fe(III) and Cr(III) complexes were investigated both experimentally and theoretically. The geometries were optimized at BP86/TZVP level. The most stable spin states were computed as doublet and quartet for Fe(magneson)_3 and Cr(magneson)_3 complexes, respectively. Time-dependent density functional theory (TDDFT) was employed to explore the absorption spectra properties, whereas the solvent effects were taken into account using the polarizable continuum model (PCM). The M06, B3LYP, and PBE0 hybrid functionals together with TZVP/LANL2TZ basis sets were used for comparing the results with experimental data. The theoretical analysis of electronic structure …
First-Principles Study Of The Electric Field Effect On The Water-Adsorbed Rutile Titanium Dioxide Surface, Abraham L. Hmiel
First-Principles Study Of The Electric Field Effect On The Water-Adsorbed Rutile Titanium Dioxide Surface, Abraham L. Hmiel
Legacy Theses & Dissertations (2009 - 2024)
TiO2 is a semiconducting material that has been used extensively in many industrial applications, and recently has become a candidate for photocatalytic water splitting, fuel cell anode support materials, sensors, and other novel nanodevices. The interface of TiO2 with water, historically well-studied but still poorly understood, presents a ubiquitous environmental challenge towards the ultimate practical usefulness of these technologies. Ground-state density functional theory (DFT) calculations studying the characteristics of molecular adsorption on model surfaces have been studied for decades, showing constant improvement in the description of the energetics and electronic structure at interfaces. These simulations are invaluable in the …
Nature Of Second-Order Nonlinear Optical Response In Phthalocyanine Derivatives: A Density Functional Theory Study, Chiming Wang, Chao Chen, Qingqi Zhang, Dongdong Qi, Jianzhuang Jiang
Nature Of Second-Order Nonlinear Optical Response In Phthalocyanine Derivatives: A Density Functional Theory Study, Chiming Wang, Chao Chen, Qingqi Zhang, Dongdong Qi, Jianzhuang Jiang
Turkish Journal of Chemistry
Density functional theory was employed to investigate a series of phthalocyanine derivatives, discovering the limitation when the expansion of the conjugated system was employed to improve the hyper-Rayleigh scattering response coefficient. Furthermore, an unusually C_{\infty v}-type octupolar population was found by electrostatic potential analysis. In addition, the dynamic and static hyper-Rayleigh scattering responses (\beta_{HRS}) were simulated using the coupled perturbed density functional theory, showing an increasing dynamic \beta_{HRS} value along with an increase in incident light energy.
Zinc Environment In Proteins: The Flexible And Reactive Core Of Hiv-1 Ncp7 And The Inhibitory Site Of Caspase-3, A. Gerard Daniel
Zinc Environment In Proteins: The Flexible And Reactive Core Of Hiv-1 Ncp7 And The Inhibitory Site Of Caspase-3, A. Gerard Daniel
Theses and Dissertations
Zinc is an essential cofactor of several proteins. The roles of zinc in these proteins are classified as catalytic, structural or regulatory. Zinc present in structural sites is considered to be a chemically inert, static structural element. On the contrary, previous studies on a C2H2 type zinc finger model compound and the C3H type HIV-1 NCp7 C-terminal zinc knuckle have shown that zinc at these sites can undergo coordination sphere expansion under the influence of a Pt based electrophile. The pentacoordination observed around zinc in these experiments raises an important question: are the structural zinc motifs found in the proteins …
Molecular Dynamics Simulations Using Advanced Sampling And Polarizable Force Fields, Tugba Kucukkal
Molecular Dynamics Simulations Using Advanced Sampling And Polarizable Force Fields, Tugba Kucukkal
All Dissertations
Molecular dynamics (MD) simulations were carried out for aqueous dipeptides, water over self-assembled monolayer (SAM) surfaces, and the nicotinic acetylcholine receptor (nAChR) ion channel. The main goal is to use advanced methods to increase the accuracy of molecular dynamics simulations while seeking solutions to problems relevant to chemistry, biophysics and materials science. In addition, activation energies of several cyclodimerization reactions were studied quantum mechanically. The simulations of the aqueous dipeptides and SAM surfaces involve modeling and detailed analysis of interfacial water, which is of interest to a range of fields from biology to materials science. For example, water has a …
Binding Energies And Solvation Of Organic Molecular Ions, Reactions Of Transition Metal Ions With, And Plasma Discharge Ionization Of Molecular Clusters, Isaac Kwame Attah
Binding Energies And Solvation Of Organic Molecular Ions, Reactions Of Transition Metal Ions With, And Plasma Discharge Ionization Of Molecular Clusters, Isaac Kwame Attah
Theses and Dissertations
In this dissertation, different approaches have been employed to address the quest of understanding the formation and growth mechanisms of carbon-containing molecular ions with relevance to astrochemistry. Ion mobility mass spectrometry and DFT computations were used to investigate how a second nitrogen in the pyrimidine ring will affect the formation of a covalent bond between the benzene radical cation and the neutral pyrimidine molecule, after it was shown that a stable covalent adduct can be formed between benzene radical cation and the neutral pyridine. Evidence for the formation of a more stable covalent adduct between the benzene radical cation and …
A Dft Study Of Vibrational Spectra And Mutagenicity Predictions Of Mononitrated Fluoranthenes [Abstract], Kefa Karimu Onchoke, Jorge Ojeda
A Dft Study Of Vibrational Spectra And Mutagenicity Predictions Of Mononitrated Fluoranthenes [Abstract], Kefa Karimu Onchoke, Jorge Ojeda
Faculty Publications
No abstract provided.
Synthesis, Characterization, And Dft Calculation Of A Pd(Ii) Schiff Base Complex, Alireza Akbari, Zahra Alinia
Synthesis, Characterization, And Dft Calculation Of A Pd(Ii) Schiff Base Complex, Alireza Akbari, Zahra Alinia
Turkish Journal of Chemistry
The 4-((E)-(2-((E)-2, 4-dihydroxybenzylideneamino) ethylimino) methyl) benzene-1,3-diol tetradentate ligand, H_2L, reacted with PdCl_2 to produce the related complex. The complex was characterized by elemental analysis, infrared and electronic spectroscopy, thermogravimetric study, and molar conductance. Furthermore, the fully optimized geometries were calculated using the ADF 2009.01 package. Comparison between the calculated and experimental results covering molecular structures, assignment of fundamental vibrational modes, and thermodynamic properties were investigated. The optimized molecular geometries were compared with the experimental data obtained from X-ray data of a similar complex, which indicated that the theoretical results agree with the corresponding experimental values. The UV-Vis spectrum of the …
A Proposed Palladium-Catalyzed Cycle For The Epoxidation Of Alkenes, Marie Vernell Parkes
A Proposed Palladium-Catalyzed Cycle For The Epoxidation Of Alkenes, Marie Vernell Parkes
Chemistry and Chemical Biology ETDs
Epoxides are an important chemical functional group, used in a wide variety of processes, from the small-scale production of pharmaceuticals to the large-scale production of propylene oxide. Current methods for production of epoxides require costly multi-step syntheses that use toxic or explosive reagents, result in low yields, and produce co-products that must be removed and often disposed. The development of an atom-efficient general method, preferably catalytic, for converting alkenes to epoxides using safe, cheap, and readily available molecular oxygen as the stoichiometric oxidant would be a great advance in both industrial and academic chemistry. Presented here is a proposed catalytic …
A Density Functional Theory And Laser Flash Photolysis Investigation Of Carbofuran Photodegradation In Aqueous Medium, A. Atifi, M. Talipov, H. Mountacer, Michael D. Ryan, M. Sarakha
A Density Functional Theory And Laser Flash Photolysis Investigation Of Carbofuran Photodegradation In Aqueous Medium, A. Atifi, M. Talipov, H. Mountacer, Michael D. Ryan, M. Sarakha
Chemistry Faculty Research and Publications
Density functional theory (DFT) approach was used to study the photodegradation of Carbofuran in aqueous medium. This computational method enables us to assign the electronic transitions and interpret the dissociative behavior upon irradiation based on a thermodynamical analysis of the bond dissociation energies (BDE) of Carbofuran. According to these calculations, phenoxy C---O bond appears weaker than the C---N bonds. Hence, it was predicted that the photodegradation of Carbofuran should occur with an initial homolytic dissociation of the C---O bond of the carbamate moiety. Laser Flash Photolysis (LFP) results clearly indicate the formation of the phenoxyl radical, which support the outcome …
Nabr Poisoning Of Au/Tio2 Catalysts: Effects On Kinetics, Poisoning Mechanism, And Estimation Of The Number Of Catalytic Active Sites, Bert D. Chandler, Shane Kendell, H. Doan, Rachel Korkosz, L. C. Grabow, Christopher J. Pursell
Nabr Poisoning Of Au/Tio2 Catalysts: Effects On Kinetics, Poisoning Mechanism, And Estimation Of The Number Of Catalytic Active Sites, Bert D. Chandler, Shane Kendell, H. Doan, Rachel Korkosz, L. C. Grabow, Christopher J. Pursell
Chemistry Faculty Research
Sodium bromide was used to intentionally poison a commercial Au/TiO2 catalyst with the goals of understanding the nature of halide poisoning and evaluating the number and nature of the catalytic active sites. A series of eight poisoned catalysts were prepared by impregnating the parent catalyst with methanolic solutions of NaBr. Each catalyst was tested with CO oxidation catalysis under differential reactor conditions; O2 reaction orders and Arrhenius activation energies were determined for each material. All of the kinetic data, including a Michaelis−Menten analysis, indicated that the primary effect of adding NaBr was to reduce the number of catalytically active sites. …
Ni_{55} Nanocluster: A Density Functional Theory Study Of The Binding Energy Of Nickel And Ethylene Adsorption, Nusret Duygu Yilmazer, Mehmet Ferdi̇ Fellah, Işik Önal
Ni_{55} Nanocluster: A Density Functional Theory Study Of The Binding Energy Of Nickel And Ethylene Adsorption, Nusret Duygu Yilmazer, Mehmet Ferdi̇ Fellah, Işik Önal
Turkish Journal of Chemistry
Ethylene adsorption on a Ni_{55} nanocluster was studied by means of the density functional theory (DFT)/B3LYP using the basis sets of 6-31G(d,p) and 86-411(41d)G in Gaussian 03. The Ni_{55} nanocluster was found to have a distorted icosahedral geometry, in accordance with the experimental findings. The binding energy value for the Ni_{55} nanocluster was calculated to be 3.51 eV/atom using equilibrium geometry calculations. The estimated bulk nickel binding energy was in reasonable agreement with the experimental value (4.85 versus 4.45 eV/atom). In addition, equilibrium geometry calculations were performed for ethylene adsorption on the Ni_{55} nanocluster for 2 different coordination numbers of …
Applications Of Density Functional Theory In Materials Science And Engineering, Manuel Alvarado
Applications Of Density Functional Theory In Materials Science And Engineering, Manuel Alvarado
Open Access Theses & Dissertations
Density Functional Theory (DFT) is a powerful tool that can be used to model various systems in materials science. Our research applies DFT to two problems of interest. First, an organic/inorganic complex dye system known as a Mayan pigment is modeled to determine chemical binding sites, verifying each model with physical data such as UV/Vis spectra. Preliminary studies on palygorskite-based mayan pigments (mayacrom blue, mayacrom purple) show excellent agreement with experimental studies when using a dimer dye geometry binding with tetrahedrally-coordinated aluminum impurity sites in palygorksite. This approach is applied to a sepiolite-based organic/inorganic dye system using thioindigo attached to …
Density Functional Theory Calculations On Hydrated Dimethylarsinic Acid And Iron Oxide Clusters, Adrian Adamescu
Density Functional Theory Calculations On Hydrated Dimethylarsinic Acid And Iron Oxide Clusters, Adrian Adamescu
Theses and Dissertations (Comprehensive)
Dimethylarsinic Acid (DMA) or (CH3)2AsO2H is an important organoarsenical compound detected in arsenic speciation studies of environmental samples and synthesized during pyrolysis of oil shale. DMA was used historically as a herbicide on large agricultural fields and can be detected in the leachates of landfills rich in waste containing arsenic such as glass, alloys, and semiconductors, as well as biologically pre-treated municipal solid waste. Under certain soil conditions DMA can become bio-available and has the potential to be recycled to more toxic inorganic forms of arsenic. Bioavailability of DMA is largely controlled by the …
Electronic States In Layered Si/Sio2/Mos2 Nanostructures, Luis Edgardo Luciano^, Domingo Ferrer, Russell R. Chianelli, Manuel Ramos*
Electronic States In Layered Si/Sio2/Mos2 Nanostructures, Luis Edgardo Luciano^, Domingo Ferrer, Russell R. Chianelli, Manuel Ramos*
COURI Symposium Abstracts, Summer 2011
No abstract provided.
Spectroscopic And Electronic Structure Studies Of Metalloenzyme Active Sites, Joseph Sempombe
Spectroscopic And Electronic Structure Studies Of Metalloenzyme Active Sites, Joseph Sempombe
Chemistry and Chemical Biology ETDs
This work reports on the electronic and geometric structural studies of xanthine oxidoreductase (XO), S-ribosylhomocysteinase (LuxS) and inducible nitric oxide synthase (iNOS) active sites resulting from the joint applications of electronic absorption, electron paramagnetic resonance and magnetic circular dichroism spectroscopic methods. XO catalyzes formal oxygen atom insertion into a substrate C-H bond, but differs from monooxygenase enzymes in that the inserted oxygen atom derives from metal activated water and reducing equivalents are generated rather than consumed. Studies on aldehyde inhibited' XO (a paramagnetic form observed during XO catalysis), analyzed in terms of the relationships between the g-, 95,97Mo hyperfine, …
Spectroscopic And Electronic Structure Studies Of Bis-Metallodithiolenes, Regina Peter Mtei
Spectroscopic And Electronic Structure Studies Of Bis-Metallodithiolenes, Regina Peter Mtei
Chemistry and Chemical Biology ETDs
Dimethylsulfoxide reductase (DMSOR) enzyme family members catalyze oxygen atom transfer to or from organic or inorganic substrate and play important roles in the global cycles of sulfur and nitrogen, as well as the detoxification of arsenite. This enzyme has recently been subject of investigation due to its catalytic nature of oxygen atom transfer. This work reports on the electronic structure and reactivity properties of dimethylsulfoxide reductase enzyme studied using spectroscopic and computational methods. The spectroscopic methods included electronic absorption (EA), electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD) and resonance Raman rRaman). Here, we report full characterization of the DMSOR …
Computational Investigation Of The Bioactive Selenium Compounds Ebselen And Selenious Acid, Sonia Antony
Computational Investigation Of The Bioactive Selenium Compounds Ebselen And Selenious Acid, Sonia Antony
Chemistry & Biochemistry Theses & Dissertations
Selenium, a toxic element, is required in trace quantities for the proper functioning of biological systems. The experimental mechanistic study of the reactions of ebselen and selenious acid is difficult due to complexity of the reaction mixtures and the presence of short-lived intermediates. Computational modeling of the reactivity of these species can give us an insight into their mechanisms, but the process is complicated by proton exchanges associated with the mechanistic steps. In gas phase modeling, this may be corrected to a certain level using the solvent assisted proton exchange (SAPE) method. SAPE is a modeling technique that mimics solvent …
E)--2--Acetyl--4--(4--Methoxyphenyldiazenyl) Phenol: X--Ray And Dft--Calculated Structure, Serap Yazici, Çi̇ğdem Albayrak, İsmai̇l Erdem Gümrükçüoğlu, İsmet Şenel, Orhan Büyükgüngör
E)--2--Acetyl--4--(4--Methoxyphenyldiazenyl) Phenol: X--Ray And Dft--Calculated Structure, Serap Yazici, Çi̇ğdem Albayrak, İsmai̇l Erdem Gümrükçüoğlu, İsmet Şenel, Orhan Büyükgüngör
Turkish Journal of Chemistry
The crystal structure of the title compound, (E)-2-acetyl-4-(4-methoxyphenyldiazenyl) phenol, displays a trans configuration of the azo moiety as found for other azo (diazene) derivatives. The aromatic mean planes are nearly coplanar and the dihedral angle between the 2 aromatic rings is 3.04(8)°. The molecules, with strong intramolecular O--H...O hydrogen bonding, are linked by weak van der Waals interactions in the 3-dimensional network. The molecular geometry, determined using X-ray diffraction techniques, was also calculated with the density functional theory (DFT), employing the hybrid exchange-correlation functional B3LYP. Experimental and theoretical IR spectra of the compound were also calculated for comparison. The results …
Density Functional Theory Studies Of Surface-Enhanced Raman Spectroscopy In Electrochemical Interfaces, Liu-Bin Zhao, De-Yin Wu, Bin Ren, Zhong-Qun Tian
Density Functional Theory Studies Of Surface-Enhanced Raman Spectroscopy In Electrochemical Interfaces, Liu-Bin Zhao, De-Yin Wu, Bin Ren, Zhong-Qun Tian
Journal of Electrochemistry
Quantum chemical density functional theory and Raman scattering theory were used to study the bonding mechanism and surface-enhanced Raman spectroscopy of pyridine adsorbed on transition metals (Ⅷ group) and coinage metals (IB group) . SERS studies of pyridine-metal systems have been reviewed. Chemical bonding mechanism as well as photo-driven charge transfer mechanism was considered to investigate the vibrational frequency shift and the enhancement of SERS intensity in electrochemical interfaces. Our theoretical results can be used to interpret the SERS phenomena dependent on metals,excitation wavelengths,and applied potentials.
15N Solid-State Nmr Detection Of Flavin Perturbation By H-Bonding In Models And Enzyme Active Sites, Dongtao Cui
15N Solid-State Nmr Detection Of Flavin Perturbation By H-Bonding In Models And Enzyme Active Sites, Dongtao Cui
University of Kentucky Doctoral Dissertations
Massey and Hemmerich proposed that the different reactivities displayed by different flavoenzymes could be achieved as a result of dominance of different flavin ring resonance structures in different binding sites. Thus, the FMN cofactor would engage in different reactions when it had different electronic structures. To test this proposal and understand how different protein sites could produce different flavin electronic structures, we are developing solid-state NMR as a means of characterizing the electronic state of the flavin ring, via the 15N chemical shift tensors of the ring N atoms. These provide information on the frontier orbitals. We propose that …
Electrocatalysis In Polymer Electrolyte Membrane Fuel Cells, Li Li, Si-Guo Chen, Xue-Qiang Qi, Yao-Qiong Wang, Meng-Bo Ji, Lan-Lan Li, Zi-Dong Wei
Electrocatalysis In Polymer Electrolyte Membrane Fuel Cells, Li Li, Si-Guo Chen, Xue-Qiang Qi, Yao-Qiong Wang, Meng-Bo Ji, Lan-Lan Li, Zi-Dong Wei
Journal of Electrochemistry
This review presents the study of Chongqing University in electrocatalysis for polymer electrolyte membrane fuel cells(PEMFCs).Based on the understanding to the performance degradation of PEMFCs' catalysts,the university has being concentrated on how to increase the activity,stability and utility of noble metal catalysts.It covers the molecular design of near-surface alloy catalysts for improvement of activity to oxygen reduction reaction(ORR) and resistance to foreign poison species,selective deposition of Pt on the so-called "three-phase interface" for a high Pt utility,and invention of anti-flooding electrode against water flooding in the catalyst layer of the membrane assemble electrode(MEA),and so on.The catalytic mechanism of electrode reactions …
A Density Functional Theory Study Of Oxidation Of Benzene To Phenol By N_2o On Fe- And Co-Zsm-5 Clusters, Mehmet Ferdi̇ Fellah, Işik Önal
A Density Functional Theory Study Of Oxidation Of Benzene To Phenol By N_2o On Fe- And Co-Zsm-5 Clusters, Mehmet Ferdi̇ Fellah, Işik Önal
Turkish Journal of Chemistry
Density functional theory (DFT) calculations were carried out in the study of oxidation of benzene to phenol by N_2O on relaxed [(SiH_3)_4AlO_4M] (where M=Fe, Co) cluster models representing Fe- and Co-ZSM-5 surfaces. The catalytic cycle steps are completed for both Fe-ZSM-5 and Co-ZSM-5 clusters. The general trend of the results that were obtained in terms of activation barriers for the Fe-ZSM-5 cluster is in agreement with the experimental and theoretical literature. It was observed that the phenol formation step is the rate-limiting step for both clusters and Co-ZSM-5 surface has a lower activation barrier than the Fe-ZSM-5 surface (i.e. 35.82 …
Quantum Chemical Investigations Of Nucleophilic Aromatic Substitution Reactions And Acid Dissociations Of Aliphatic Carboxylic Acids, David Henry Schory
Quantum Chemical Investigations Of Nucleophilic Aromatic Substitution Reactions And Acid Dissociations Of Aliphatic Carboxylic Acids, David Henry Schory
Browse all Theses and Dissertations
Quantum chemical analysis was used to examine nucleophilic aromatic substitution reactions of fluorinated benzophenones, diphenyl sulfones, and triphenylphosphine oxides. Some experimental results for these compounds were contrary to conventional wisdom, which holds that calculated atomic charges for the aromatic sites and 13C-NMR and 19F-NMR chemical shifts should allow prediction of the preferred sites for aromatic substitution. Density functional theory (B3LYP/6-31+G*//RM1) and semi-empirical (RM1) quantum chemical calculations were employed to study the intermediates in the reaction pathways in order to identify the preferred paths for aromatic substitution. In most cases studied para substitution pathways had the lower energy intermediates …
Hydrogenase Inhibition By O2: Density Functional Theory/Molecular Mechanics Investigation, Daniela Dogaru
Hydrogenase Inhibition By O2: Density Functional Theory/Molecular Mechanics Investigation, Daniela Dogaru
ETD Archive
[Fe-Fe]-hydrogenases are enzymes that reversibly catalyze the reduction of protons to molecular hydrogen, which occurs in anaerobic media. In living systems, [Fe-Fe]-hydrogenases shift the reversible reaction towards H2 formation. The [Fe-Fe]-hydrogenase H-cluster is the active site, which contains two iron atoms (Fep-Fed, i.e., proximal and distal iron). Because most experimental and theoretical investigations confirm that the structure of di-iron air inhibited species is FepII-FedII-O-O-H-, O2 has to be prevented from binding to Fed in all di-iron subcluster oxidation states in order to retain a catalytically active enzyme. By understanding the catalytic processes of metalloenzymes, researches are enabled to produce an …
A Theoretical Study For The Reactivation Of O2 Inhibited [Fe-Fe]-Hydrogenase, Stefan Motiu
A Theoretical Study For The Reactivation Of O2 Inhibited [Fe-Fe]-Hydrogenase, Stefan Motiu
ETD Archive
The current investigation presents a reactivation pathway of the exogenously inhibited H-cluster (viz., by O2, or OH-, which metabolizes to H2O), for both vacuum and aqueous enzyme phase. The H-cluster is the catalytic site of [Fe-Fe]-hydrogenase, with the latter extracted from Desulfovibrio desulfuricans (Dd) bacteria. It consists of proximal iron, Fep, and distal Fed subunit, [Fep-Fed], which is bridged by di(thiomethyl)amine (DTMA) ligand, and a proximal cubane subunit, [Fe4-S4]2+p. [Fep-Fed] is coordinated by two cyanides (CN-), two terminal carbonyls (COt), and a bridging carbonyl (COb)*. An Fe atom from [Fe4-S4]2+p connects Fep through a cysteinyl sulfur (of Cys382). Density functional …
Activation Of Light Alkanes On Pure And Fe And Al Doped Silica Clusters: A Density Functional And Oniom Study, Mehmet Ferdi̇ Fellah, Işik Önal
Activation Of Light Alkanes On Pure And Fe And Al Doped Silica Clusters: A Density Functional And Oniom Study, Mehmet Ferdi̇ Fellah, Işik Önal
Turkish Journal of Chemistry
C-H bond activation was studied by use of density functional theory (DFT) and ONIOM calculations as implemented in Gaussian 2003 at the B3LYP level utilising 6-31G* as the basis set for Si, Al, and Fe atoms and 3-21G** as the basis set for O and H atoms. Relative energy profiles were determined for pure silica modeled by a Si_7O_{21} cluster and Fe and Al doped silica clusters via coordinate driving calculations. The activation barriers for C-H bond activation of methane and ethane decrease with the substitution of Fe on the silica surface, which theoretically demonstrates a favorable effect of Fe …
Ab Initio Molecular Dynamics Simulations Of Methylaluminoxane (Mao) Synthesis By Hydrolysis Of Trimethylaluminum, Lacramioara Negureanu
Ab Initio Molecular Dynamics Simulations Of Methylaluminoxane (Mao) Synthesis By Hydrolysis Of Trimethylaluminum, Lacramioara Negureanu
LSU Doctoral Dissertations
MAO is the co-catalyst in the metallocene catalytic systems, which are widely used in single site olefin polymerization due to their high stereoselectivity. To date, the precise structure of MAO, the particular compound or compounds catalytically active in MAO, have eluded researchers. MAO, a white amorphous powder, is not a good sample for a direct spectroscopic characterization, and its NMR spectra are broad and almost featureless. Many structural models have been proposed but none are generally accepted. In the first part of this work the MAO formation mechanism was addressed. Molecular dynamics simulations at MP2 configuration interaction theory level have …
Potential Energy Surface Around The Tropylium Ion., Kenneth Wayne Bullins
Potential Energy Surface Around The Tropylium Ion., Kenneth Wayne Bullins
Electronic Theses and Dissertations
The formation of the tropylium ion, C7H7+, in the mass spectrum of toluene is a chemical process that has been studied extensively in the past. The advances in computational power of personal computers have made the investigation of the pathway to form this ion and its subsequent decomposition feasible at a fairly high level of theory. The calculations that we performed were at the HF/6-31G (d, p) and the B3LYP/6-311++G (2d) levels. This work will show areas of the potential energy surface around the highly symmetric tropylium ion to give a glance of possible mechanisms …