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Mechanical Calculations (mechanical + calculation)
Kinds of Mechanical Calculations Selected AbstractsAustenitic Stainless Steels from Quantum Mechanical Calculations,ADVANCED ENGINEERING MATERIALS, Issue 4 2004L. Vitos Quantum mechanics is used to study the influence of the chemical composition on the elastic properties of austenitic stainless steels. Fe based alloys comprising approximately 15% Cr and 8% Ni are predicted to have the largest hardness among the usual austenitic steels, which, however, is associated with increased brittleness and susceptibility to various forms of localized corrosion. It is shown that few percent of additional Os or Ir to Fe15Cr8Ni alloy significantly improve on both of these shortcomings, without deteriorating the hardness. [source] Quantum Mechanical Calculations of Conformationally Relevant 1H and 13C,NMR Chemical Shifts of N-, O-, and S-Substituted Calixarene SystemsCHEMISTRY - A EUROPEAN JOURNAL, Issue 25 2007Giuseppe Bifulco Prof. Abstract QM GIAO calculations of 13C and 1H chemical shift values of the ArCH2Ar group in N-, O-, and S-substituted calixarene systems were performed with a hybrid DFT functional MPW1PW91 and 6-31G(d,p) basis set. A good reproduction of experimental data was obtained for some representative calixarenes and for a series of simplified calixarene models. This allowed the derivation of chemical shift surfaces versus , and , dihedral angles. The applicability of chemical shift surfaces in the study of calixarene conformational features is illustrated. [source] Fast fragments: The development of a parallel effective fragment potential methodJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 15 2004Heather M. Netzloff Abstract The Effective Fragment Potential (EFP) method for solvation decreases the cost of a fully quantum mechanical calculation by dividing a chemical system into an ab initio region that contains the solute plus some number of solvent molecules, if desired, and an "effective fragment" region that contains the remaining solvent molecules. Interactions introduced with this fragment region (for example, Coulomb and polarization interactions) are added as one-electron terms to the total system Hamiltonian. As larger systems and dynamics are just starting to be studied with the EFP method, more needs to be done to decrease the calculation time of the method. This article considers parallelization of both the EFP fragment-fragment and mixed quantum mechanics (QM)-EFP interaction energy and gradient computation within the GAMESS suite of programs. The iteratively self-consistent polarization term is treated with a new algorithm that makes use of nonblocking communication to obtain better scalability. Results show that reasonable speedup is achieved with a variety of sizes of water clusters and number of processors. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1926,1935, 2004 [source] Structural Changes in the BODIPY Dye PM567 Enhancing the Laser Action in Liquid and Solid Media,ADVANCED FUNCTIONAL MATERIALS, Issue 16 2007I. García-Moreno Abstract In the search for more efficient and photostable solid-state dye lasers, newly synthesized analogs of the borondipyrromethene (BODIPY) dye PM567, bearing the polymerizable methacryloyloxypropyl group at position 2 (PMoMA) or at positions 2 and 6 (PDiMA), have been studied in the form of solid copolymers with methyl methacrylate (MMA). The parent dye PM567, as well as the model analogs bearing the acetoxypropyl group in the same positions, PMoAc and PDiAc, respectively, have been also studied both in liquid solvents and in solid poly(MMA) (PMMA) solution. Although in liquid solution PMoAc and PDiAc have the same photophysical properties as PM567, PDiAc exhibited a photostability up to 10 times higher than that of PM567 in ethanol under 310,nm-irradiation. The possible stabilization factors of PDiAc have been analyzed and discussed on the basis of the redox potentials, the ability for singlet molecular oxygen [O2(1,g)] generation, the reactivity with O2(1,g), and quantum mechanical calculations. Both PMoAc and PDiAc, pumped transversally at 532,nm, lased in liquid solution with a high (up to 58,%), near solvent-independent efficiency. This enhanced photostabilization has been also observed in solid polymeric and copolymeric media. While the solid solution of the model dye PDiAc in PMMA showed a lasing efficiency of 33,%, with a decrease in the laser output of ca.,50,% after 60,000 pump pulses (10,Hz repetition rate) in the same position of the sample, the solid copolymer with the double bonded chromophore, COP(PDiMA-MMA), showed lasing efficiencies of up to 37,%, and no sign of degradation in the laser output after 100,000 similar pump pulses. Even under the more demanding repetition rate of 30,Hz, the laser emission from this material remained at 67,% of its initial laser output after 400,000 pump pulses, which is the highest laser photostability achieved to date for solid-state lasers based on organic polymeric materials doped with laser dyes. This result indicates that the double covalent linkage of the BODIPY chromophore to a PMMA polymeric matrix is even more efficient than the simple linkage, for its photostabilization under laser operation. [source] Hydroxyl radical reactions with halogenated ethanols in aqueous solution: Kinetics and thermochemistryINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2008I. Morozov Laser flash photolysis combined with competition kinetics with SCN, as the reference substance has been used to determine the rate constants of OH radicals with three fluorinated and three chlorinated ethanols in water as a function of temperature. The following Arrhenius expressions have been obtained for the reactions of OH radicals with (1) 2-fluoroethanol, k1(T) = (5.7 ± 0.8) × 1011 exp((,2047 ± 1202)/T) M,1 s,1, (2) 2,2-difluoroethanol, k2(T) = (4.5 ± 0.5) × 109 exp((,855 ± 796)/T) M,1 s,1, (3) 2,2,2-trifluoroethanol, k3(T) = (2.0 ± 0.1) × 1011 exp((,2400 ± 790)/T) M,1 s,1, (4) 2-chloroethanol, k4(T) = (3.0 ± 0.2) × 1010 exp((,1067 ± 440)/T) M,1 s,1, (5) 2, 2-dichloroethanol, k5(T) = (2.1 ± 0.2) × 1010 exp((,1179 ± 517)/T) M,1 s,1, and (6) 2,2,2-trichloroethanol, k6(T) = (1.6 ± 0.1) × 1010 exp((,1237 ± 550)/T) M,1 s,1. All experiments were carried out at temperatures between 288 and 328 K and at pH = 5.5,6.5. This set of compounds has been chosen for a detailed study because of their possible environmental impact as alternatives to chlorofluorocarbon and hydrogen-containing chlorofluorocarbon compounds in the case of the fluorinated alcohols and due to the demonstrated toxicity when chlorinated alcohols are considered. The observed rate constants and derived activation energies of the reactions are correlated with the corresponding bond dissociation energy (BDE) and ionization potential (IP), where the BDEs and IPs of the chlorinated ethanols have been calculated using quantum mechanical calculations. The errors stated in this study are statistical errors for a confidence interval of 95%. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 174,188, 2008 [source] Non,Born,Oppenheimer calculations of the ground state of H3INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 14 2007Mauricio Cafiero Abstract We present quantum,mechanical calculations for the ground state of the H3 system performed without the Born-Oppenehimer approximation. In the calculations we use explicitly correlated Gaussian basis functions that explicitly depend on all of the interparticle distances. These basis functions allow us to achieve high accuracy while explicitly describing nucleus,nucleus, nucleus,electron, and electron,electron correlation effects. Gaussian basis sets ranging in size from 85 to 950 functions have been optimized using a gradient-based procedure. The issue of defining and extracting the H3 molecular structure based on the non-BO wave function is also discussed. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Memory Effects in Palladium-Catalyzed Allylic Alkylations of 2-Cyclohexen-1-yl AcetateADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 17-18 2007Nina Svensen Abstract The objective of this work was to characterize the enantiospecificity of the allylic alkylation of enantioenriched 2-cyclohexen-1-yl acetate with the enolate ion of dimethyl malonate catalyzed by unsymmetrical palladium catalysts. The precatalysts employed were (,3 -allyl)PdLCl, where L is a monophosphine ligand [PPh3, PCy3, P(2-BiPh)Cy2, or P(t- Bu)3], all of which afforded enantiospecificity to some extent (5,47,%). Quantum mechanical calculations show that, theoretically, the enantiospecificity should be high due to a preference for the "trans to P" transition state in both formation of the ,3 -allyl intermediate and nucleophilic attack. However, the observed enantiospecificity is relatively low due to isomerization of the ,3 -allyl intermediate and/or dynamic equilibria between the catalytically active (,3 -allyl)PdLCl species and [(,3 -allyl)PdL2]+ or [(,3 -allyl)PdCl]2. It was also observed experimentally that increasing the bulk of the phosphine inhibits formation of the [(,3 -allyl)PdL2]+ complexes, significantly increasing the observed enantiospecificity for some of the ligands. [source] Ab initio computational study of positron emission tomography ligands interacting with lipid molecule for the prediction of nonspecific bindingJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 14 2008Lula Rosso Abstract Nonspecific binding is a poorly understood biological phenomenon of relevance in the study of small molecules interactions in vivo and in drug development. Nonspecific binding is thought to be correlated in part to a molecule's lipophilicity, typically estimated by measuring (or calculating) octanol,water partition coefficient. This is, however, a gross simplification of a complex phenomenon. In this article, we present a computational method whose aim is to help identify positron emission tomography (PET) ligands with low nonspecific binding characteristics by investigating the molecular basis of ligand,membrane interaction. We considered a set consisting of 10 well-studied central nervous system PET radiotracers acting on a variety of molecular targets. Quantum mechanical calculations were used to estimate the strength of the interaction between each drug molecule and one phospholipid molecule commonly present in mammalian membranes. The results indicate a correlation between the computed drug,lipid interaction energy and the in vivo nonspecific distribution volume relative to the free tracer plasma concentration, calculated using standard compartmental modeling for the analysis of PET data. Significantly, the drugs whose interaction with the lipid molecule more favorably possessed, in general, a higher nonspecific binding value, whereas for the drugs taken in consideration in this study, the water-octanol partition coefficient, log P, did not show good predictive power of the nonspecific binding. This study also illustrates how ab initio chemical methods may offer meaningful and unbiased insights for the understanding of the underlying chemical mechanisms in biological systems. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008 [source] Dynamic structures of phosphodiesterase-5 active site by combined molecular dynamics simulations and hybrid quantum mechanical/molecular mechanical calculationsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 8 2008Ying Xiong Abstract Various quantum mechanical/molecular mechanical (QM/MM) geometry optimizations starting from an x-ray crystal structure and from the snapshot structures of constrained molecular dynamics (MD) simulations have been performed to characterize two dynamically stable active site structures of phosphodiesterase-5 (PDE5) in solution. The only difference between the two PDE5 structures exists in the catalytic, second bridging ligand (BL2) which is HO, or H2O. It has been shown that, whereas BL2 (i.e. HO,) in the PDE5(BL2 = HO,) structure can really bridge the two positively charged metal ions (Zn2+ and Mg2+), BL2 (i.e. H2O) in the PDE5(BL2 = H2O) structure can only coordinate Mg2+. It has been demonstrated that the results of the QM/MM geometry optimizations are remarkably affected by the solvent water molecules, the dynamics of the protein environment, and the electronic embedding charges of the MM region in the QM part of the QMM/MM calculation. The PDE5(BL2 = H2O) geometries optimized by using the QM/MM method in different ways show strong couplings between these important factors. It is interesting to note that the PDE5(BL2 = HO - ) and PDE5(BL2 = H2O) geometries determined by the QM/MM calculations neglecting these three factors are all consistent with the corresponding geometries determined by the QM/MM calculations that account for all of these three factors. These results suggest the overall effects of these three important factors on the optimized geometries can roughly cancel out. However, the QM/MM calculations that only account for some of these factors could lead to considerably different geometries. These results might be useful also in guiding future QM/MM geometry optimizations on other enzymes. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008 [source] Stochastic search for isomers on a quantum mechanical surfaceJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 5 2004Martin Saunders Abstract In studying molecules with unusual bonding and structures, it is desirable to be able to find all the isomers that are minima on the energy surface. A stochastic search procedure is described for seeking all the isomers on a surface defined by quantum mechanical calculations involving random kicks followed by optimization. It has been applied to searching for singlet structures for C6 using the restricted Hartree,Fock/6-311G basis set. In addition to the linear chain and ring previously investigated, 11 additional structures (A,K) were located at this level. These provide a basis for discussing qualitative bonding motifs for this carbon cluster. The application of a similar idea to searching for transition states is discussed. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 621,626, 2004 [source] Direct hydroxide attack is a plausible mechanism for amidase antibody 43C9,JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2003Lillian T. Chong Abstract Direct hydroxide attack on the scissile carbonyl of the substrate has been suggested as a likely mechanism for esterase antibodies elicited by phosphonate haptens, which mimic the transition states for the alkaline hydrolysis of esters.1 The unique amidase activity of esterase antibody 43C9 has been attributed to nucleophilic attack by an active-site histidine residue.2 Yet, the active site of 43C9 is strikingly similar to those of other esterase antibodies, particularly 17E8. We have carried out quantum mechanical calculations, molecular dynamics simulations, and free energy calculations to assess the mechanism involving direct hydroxide attack for 43C9. Results support this mechanism and suggest that the mechanism is plausible for other antiphosphonate antibodies that catalyze the hydrolysis of (p -nitro)phenyl esters. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1371,1377, 2003 [source] Analysis of interaction modes in calix[4]arene,levofloxacin complexes by quantum methodsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 3 2006Alexandrine Lambert Abstract Host,guest interactions between chiral calix[4]arenes and the antibiotic levofloxacin are analyzed on the basis of quantum mechanical calculations at the density functional (for model systems) and semi-empirical levels. The calix[4]arene macrocycle carries two (+)-isomenthyl groups attached to opposing phenyl groups at the lower rim and different substituents (R,=,H, CH3, tBu, CH2CHCH2, COCH3 and NO2) are considered at the upper rim. Nitro derivatives are expected to form ionized complexes whereas the other derivatives should form neutral complexes with a very low stability. Copyright © 2006 John Wiley & Sons, Ltd. [source] Direct measurements of the addition and recombination of acrylate radicals: Access to propagation and termination rate constants?JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2006J. Lalevée Abstract Acrylate radicals produced by the addition of an aminoalkyl radical to five acrylate monomers were directly observed by transient absorption spectroscopy, which allowed us to easily follow their chemical reactivity. It was possible (1) to characterize their absorption in the visible part of the spectrum, (2) to calculate their absorption properties, (3) to determine the energy barriers of the addition through quantum mechanical calculations, (4) to monitor the kinetics of the subsequent addition to another monomer unit, and (5) to follow the recombination of two acrylate radicals. These two latter points could mimic the propagation and termination reactions of polymerization-propagating acrylate radicals. Methacrylate and acrylonitrile radicals were also studied. The obtained results were in good agreement with the propagation rate constants determined by the well-established pulsed laser polymerization techniques. Our method could likely provide rapid access to both the propagation and termination rate constants in suitable systems and appears to be powerful and promising for studying and comparing the reactivities of different acrylate monomer structures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3577,3587, 2006 [source] The Effect of Protonation on the Optical Properties of Conjugated Fluorene,Pyridine CopolymersMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 20 2008Stefan Kappaun Abstract A series of conjugated alternating and statistical copolymers of fluorene and pyridine are synthesized and characterized. The compounds under investigation, namely poly[2,7-(9,9-dihexylfluorenyl)- alt -(2,6-pyridinyl)] and poly[2,7-(9,9-dihexylfluorenyl)- stat -(2,6-pyridinyl)], are prepared by a Suzuki-type cross-coupling reaction starting from commercially available materials utilizing the recently described catalyst trans -bis(dicyclohexylamine) palladiumdiacetate ("DAPCy"). The target compounds are investigated by nuclear magnetic resonance and infrared spectroscopy, matrix-assisted laser desorption ionization time-of-flight mass spectrometry, thermal analysis, UV,Vis absorption spectroscopy, and luminescence measurements in solution and in the solid state. Special emphasis is placed on studying the consequences of protonation on the photophysical properties of the described materials. Achieving a concise microscopic understanding of the effects of protonation on the absorption and luminescence characteristics is crucial for potential applications in, e.g., optical sensors. To that aim, the results of the systematic studies of the photophysical properties are explained by quantum mechanical calculations. [source] Hydrogen bonds and local symmetry in the crystal structure of gibbsiteMAGNETIC RESONANCE IN CHEMISTRY, Issue 11 2010Anastasia Vyalikh Abstract First-principles quantum mechanical calculations of NMR chemical shifts and quadrupolar parameters have been carried out to assign the 27Al MAS NMR resonances in gibbsite. The 27Al NMR spectrum shows two signals for octahedral aluminum revealing two aluminum sites coordinated by six hydroxyl groups each, although the crystallographic positions of the two Al sites show little difference. The presence of two distinguished 27Al NMR resonances characterized by rather similar chemical shifts but quadrupolar coupling constants differing by roughly a factor of two is explained by different character of the hydrogen bonds, in which the hydroxyls forming the corresponding octahedron around each aluminum site, are involved. The Al-I site characterized by a CQ = 4.6 MHz is surrounded by OHgroups participating in four intralayer and two interlayer hydrogen bonds, while the Al-II site with the smaller quadrupolar constant (2.2 MHz) is coordinated by hydroxides, of which two point toward the intralayer cavities and four OH-bonds are aligned toward the interlayer gallery. In high-resolution solid-state 1H CRAMPS (combination of rotation and multiple-pulse spectroscopy) four signals with an intensity ratio of 1:2:2:1 are resolved which allow to distinguish six nonequivalent hydrogen sites reported in the gibbsite crystal structure and to ascribe them to two types of structural OH groups associated with intralayer and interlayer hydrogen bonds. This study can be applied to characterize the gibbsite-like layer,intergallery interactions associated with hydrogen bonding in the more complex systems, such as synthetic aluminum layered double hydroxides. Copyright © 2010 John Wiley & Sons, Ltd. [source] Ab Initio Quantum Chemical Investigation of the First Steps of the Photocycle of Phototropin: A Model Study,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2003Christian Neiß ABSTRACT Phototropin is a blue light,activated photoreceptor that plays a dominant role in the phototropism of plants. The protein contains two subunits that bind flavin mononucleotide (FMN), which are responsible for the initial steps of the light-induced reaction. It has been proposed that the photoexcited flavin molecule adds a cysteine residue of the protein backbone, thus activating autophosphorylation of the enzyme. In this study, the electronic properties of several FMN-related compounds in different charge and spin states are characterized by means of ab initio quantum mechanical calculations. The model compounds serve as idealized model chromophores for phototropism. Reaction energies are estimated for simple model reactions, roughly representing the addition of a cysteine residue to the flavin molecule. Excitation energies were calculated with the help of time-dependent density functional theory. On the basis of these calculations we propose the following mechanism for the addition reaction: (1) after photoexcitation of FMN out of the singlet ground state S0, excited singlet state(s) are populated; these relax to the lowest excited singlet state S1, and subsequently by intersystem crossing FMN in the lowest triplet state, T1 is formed; (2) the triplet easily removes the neutral hydrogen atom from the H,S group of the cysteine residue; and (3) the resulting thio radical is added. [source] The structural elucidation of a novel iridoid derivative from Tachiadenus longiflorus (Gentianaceae) using the LSD programme and quantum chemical computationsPHYTOCHEMICAL ANALYSIS, Issue 2 2006D. A. Mulholland Abstract Oleanolic acid, scoparone, scopoletin and a novel iridoid derivative, angelone, were isolated from Tachiadenus longiflorus (Gentianaceae). The structure of angelone was determined from NMR data, given as input to the Logic for Structure Determination Programme, and was finally confirmed by comparison of experimental 13C-NMR chemical shifts with those obtained by quantum mechanical calculations. Copyright © 2005 John Wiley & Sons, Ltd. [source] Copolymers of N -methylpyrrole and 3,4-ethylenedioxythiophene: structural, physical and electronic propertiesPOLYMER INTERNATIONAL, Issue 6 2007Cintia Ocampo Abstract The structural, electric and electronic properties of copolymers derived from mixtures of N -methylpyrrole and 3,4-ethylenedioxythiophene (EDOT) with various concentration ratios have been investigated and, additionally, compared with those of the corresponding homopolymers. The electropolymerization kinetics of all the generated copolymers and the homopolymers was examined in terms of current productivity using chronoamperometry. The chemical structure of the linkages between adjacent monomers and the microstructure of the chains were investigated using Fourier transform infrared spectroscopy and quantum mechanical calculations, respectively. The results indicate that the linkages between monomeric units formed during the anodic copolymerization are of the ,,, type, while the microstructure of the copolymers depends on the EDOT content. Theoretical calculations were also used to examine the electronic properties of the systems under study, while the conductivity and the electrical stability were studied using the sheet-resistance method. Interestingly, the electric properties are consistent with the random and block microstructures predicted for the copolymers with low and high EDOT content, respectively. Copyright © 2006 Society of Chemical Industry [source] 2,3-Dihydro-1,3-benzothiazol-2-iminium hydrogen oxydiacetate: a combined structural and theoretical studyACTA CRYSTALLOGRAPHICA SECTION C, Issue 1 2009Agata Trzesowska-Kruszynska In the title compound, C7H7N2S+·C4H5O5,, the ions are connected by N,H...O hydrogen bonds. The hydrogen oxydiacetate residues are linked together by O,H...O hydrogen bonds disordered about centres of inversion into hydrogen-bonded ribbon layers crosslinked by weak C,H...O and stacking interactions. The cation exists mainly in the 2,3-dihydro-1,3-benzothiazol-2-iminium form, with a small participation of the 2-aminobenzothiazolium form, based on the structural data and quantum mechanical calculations. This study provides structural insights relevant to the biochemical activity of benzothiazole molecules. [source] 2-Bromo-5-hydroxybenzaldehydeACTA CRYSTALLOGRAPHICA SECTION C, Issue 3 2000A. Matos Beja The molecules of the title compound, C7H5BrO2, form zigzag chains running along the b axis and are stacked in layers perpendicular to the a axis. Intermolecular bonding occurs through hydrogen bonds linking the hydroxyl and carbonyl groups, with an O,O distance of 2.804,(4),Å. The Br atom deviates significantly from the plane of the ring and the aldehyde group is twisted by 7.1,(5)° around the Csp2,Caryl bond. The geometry of the molecule in the crystal is compared to that given by ab initio quantum mechanical calculations for the isolated molecule, using a molecular orbital Hartree,Fock method and density functional theory. [source] Solvation of Uranyl(II), Europium(III) and Europium(II) Cations in "Basic" Room-Temperature Ionic Liquids: A Theoretical StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2004Alain Chaumont Abstract We report a molecular dynamics study of the solvation of UO22+, Eu3+ and Eu2+ ions in two "basic" (Lewis acidity) room-temperature ionic liquids (IL) composed of the 1-ethyl-3-methylimidazolium cation (EMI+) and a mixture of AlCl4, and Cl, anions, in which the Cl,/AlCl4, ratio is about 1 and 3, respectively. The study reveals the importance of the [UO2Cl4]2, species, which spontaneously form during most simulations, and that the first solvation shell of europium is filled with Cl, and AlCl4, ions embedded in a cationic EMI+ shell. The stability of the [UO2Cl4]2, and [EuIIICl6]3, complexes is supported by quantum mechanical calculations, according to which the uranyl and europium cations intrinsically prefer Cl, to the AlCl4, ion. In the gas phase, however, [EuIIICl6]3, and [EuIICl6]4, complexes are predicted to be metastable and to lose two to three Cl, ions. This contrasts with the results of simulations of complexes in ILs, in which the "solvation" of the europium complexes increases with the number of coordinated chlorides, leading to an equilibrium between different chloro species. The behavior of the hydrated [Eu(OH2)8]3+ complex is considered in the basic liquids; the complex exchanges H2O molecules with Cl, ions to form mixed [EuCl3(OH2)4] and [EuCl4(OH2)3], complexes. The results of the simulations allow us to better understand the microscopic nature and solvation of lanthanide and actinide complexes in "basic" ionic liquids. [source] Determining Molecular Structures and Conformations Directly from Electron Diffraction using a Genetic AlgorithmCHEMPHYSCHEM, Issue 2 2006Scott Habershon Dr. Abstract A global optimization strategy, based upon application of a genetic algorithm (GA), is demonstrated as an approach for determining the structures of molecules possessing significant conformational flexibility directly from gas-phase electron diffraction data. In contrast to the common approach to molecular structure determination, based on trial-and-error assessment of structures available from quantum chemical calculations, the GA approach described here does not require expensive quantum mechanical calculations or manual searching of the potential energy surface of the sample molecule, relying instead upon simple comparison between the experimental and calculated diffraction pattern derived from a proposed trial molecular structure. Structures as complex as all- trans retinal and p -coumaric acid, both important chromophores in photosensing processes, may be determined by this approach. In the examples presented here, we find that the GA approach can determine the correct conformation of a flexible molecule described by 11 independent torsion angles. We also demonstrate applications to samples comprising a mixture of two distinct molecular conformations. With these results we conclude that applications of this approach are very promising in elucidating the structures of large molecules directly from electron diffraction data. [source] Experimental and Theoretical Investigation of the Room-Temperature Photoluminescence of Amorphized Pb(Zr,Ti)O3CHEMPHYSCHEM, Issue 8 2005Emmanuelle Orhan Dr. Abstract Ultrafine PbZr0.20Ti0.80O3 was amorphized through high-energy mechanical milling. The structural evolution through the amorphization process was accompanied by various characterization techniques, such as X-ray diffraction, Fourier-transformed IR spectroscopy (FTIR), high-resolution transmission electron microscopy (HR-TEM), and Raman spectroscopy. A strong photoluminescence was measured at room temperature for amorphized PbZr0.20Ti0.80O3, and interpreted by means of high-level quantum mechanical calculations in the density functional theory framework. Three periodic models were used to represent the crystalline and amorphized PbZr0.20Ti0.80O3, and they allowed the calculation of electronic properties that are consistent with the experimental data and that explain the appearance of photoluminescence. [source] Determination of absolute configurations by X-ray crystallography and 1H NMR anisotropyCHIRALITY, Issue 5 2008Nobuyuki Harada Abstract To determine the absolute configurations of chiral compounds, many spectroscopic and diffraction methods have been developed. Among them, X-ray crystallographic Bijvoet method, CD exciton chirality method, and the combination of vibrational circular dichroism and quantum mechanical calculations are of nonempirical nature. On the other hand, X-ray crystallography using a chiral internal reference, and 1H NMR spectroscopy using chiral anisotropy reagents are relative and/or empirical methods. In addition to absolute configurational determinations, preparations of enantiopure compounds are strongly desired. As chiral reagents useful for both the preparation of enantiopure compounds by HPLC separation and the simultaneous determination of their absolute configurations, we have developed camphorsultam dichlorophthalic acid (CSDP acid) for X-ray crystallography and 2-methoxy-2-(1-naphthyl)propionic acid (M,NP acid) for 1H NMR spectroscopy. In this review, the principles and applications of these X-ray and NMR methods are explained using mostly our own data. Chirality, 2008. © 2007 Wiley-Liss, Inc. 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