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Ionization Potential (ionization + potential)
Selected AbstractsHigh-Performance Field-Effect Transistor Based on Dibenzo[d,d,]thieno[3,2- b;4,5- b,]dithiophene, an Easily Synthesized Semiconductor with High Ionization Potential,ADVANCED MATERIALS, Issue 19 2007H. Gao Three simple, controlled steps are all it takes to synthesize the title pentacene analogue DBTDT (see figure). The material's high ionization potential, high thermal and photostability, high mobilities, and an on/off ratio larger than 106 at a substrate temperature of ca.,36,°C, as reported here, suggest that DBTDT will be extremely valuable for applications in plastic organic electronics. [source] Topological Electronegativity Index and Its Application , I. Ionization Potentials of Alkyl Groups and Alkyl HalidesMOLECULAR INFORMATICS, Issue 9 2007Chenzhong Cao Abstract A Topological Electronegativity Index (TEI) for alkyl group was developed, based on the bond adjacency matrix of the radical atom. Taking the radical atom and the adjacency atoms (or groups) as the vertices of molecular graph of the alkyl group, the bond adjacency matrix was constructed, in which the diagonal elements were assigned the Pauling electronegativity of the atom (or group), and the off-diagonal elements were assigned values 1 or 0. The off-diagonal elements represent the bond connections: that is when the two atoms (or groups) connect with each other, it is 1; otherwise is 0. From the matrix, the eigenvalues were obtained and its geometric mean value was considered as the TEI of an alkyl. The calculated TEI has good correlation with its experimental ionization potential. Further, the TEI was applied to correlate with the ionization potentials of alkyl halides and substituted ethenes, and to correlate with the Bond Dissociation Energies (BDEs) of the CiH bonds in alkanes. [source] Ionization potentials of heteroalkenes: a comparative studyAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 12 2004Anna Chrostowska Abstract Methanimine, methylenephosphine and methylenearsine have been prepared in the gas phase and the gaseous flow has been analyzed by spectroscopy. Photoelectron spectra have been recorded and we report here a comparative study on these spectra. This comparison has been extended to the corresponding derivatives with a triple bond: hydrogen cyanide and methylidynephosphine. Estimation by theoretical calculations of the ionization potentials of the unknown methylidynearsine has been proposed. Copyright © 2004 John Wiley & Sons, Ltd. [source] Triplet Formation in Fullerene Multi-Adduct Blends for Organic Solar Cells and Its Influence on Device PerformanceADVANCED FUNCTIONAL MATERIALS, Issue 16 2010Clare Dyer-Smith Abstract In organic solar cells, high open circuit voltages may be obtained by choosing materials with a high offset between the donor highest occupied molecular orbital (HOMO) and acceptor lowest unoccupied molecular orbital (LUMO). However, increasing this energy offset can also lead to photophysical processes that compete with charge separation. In this paper the formation of triplet states is addressed in blends of polyfluorene polymers with a series of PCBM multi-adducts. Specifically, it is demonstrated that the formation of such triplets occurs when the offset energy between donor ionization potential and acceptor electron affinity is ,1.6 eV or greater. Spectroscopic measurements support a mechanism of resonance energy transfer for triplet formation, influenced by the energy levels of the materials, but also demonstrate that the competition between processes at the donor,acceptor interface is strongly influenced by morphology. [source] Quantum-Chemical Characterization of the Origin of Dipole Formation at Molecular Organic/Organic InterfacesADVANCED FUNCTIONAL MATERIALS, Issue 4 2009Igor Avilov Abstract Recent experiments have reported a vacuum level shift at the interface between organic materials due to the formation of an interface dipole layer. On the basis of quantum-chemical calculations, this paper sheds light on the factors contributing to the formation of an interface dipole between an electron donor and an electron acceptor, considering as model system a complex made of tetrathiafulvalene (TTF) as a donor and tetracyanoquinodimethane (TCNQ) as an acceptor. The results indicate that the interface dipole is governed both by charge-transfer and polarization effects and allow for disentangling of their respective contributions. Two regimes of charge transfer can be distinguished depending on the strength of the electronic coupling: a fractional charge transfer occurs in the strong coupling regime while only integer charges are transferred when the coupling is weak. The polarization contribution can be significant, even in the presence of a pronounced charge transfer between the donor and acceptor molecules. The values of ionization potential and electron affinity of the donor and acceptor molecules may experience shifts as large as several tenths of an eV at the interface with respect to the isolated compounds. [source] Design of Hole Blocking Layer with Electron Transport Channels for High Performance Polymer Light-Emitting Diodes,ADVANCED MATERIALS, Issue 10 2008Chung-Chin Hsiao A novel dual-functional composite layer composed of a high ionization potential nonconjugated polymer or conjugated molecular material and an inorganic salt of a low work function metal is demonstrated. The composite provides superior hole blocking along with promising electron transport capability and results in good device performance for two model electroluminescent polymers, PFO and MEH-PPV. [source] Novel Thiophene-Thiazolothiazole Copolymers for Organic Field-Effect Transistors,ADVANCED MATERIALS, Issue 23 2007I. Osaka A semiconducting polymer bearing the thiazolothiazole moiety in the polythiophene backbone (see figure) is synthesized. The polymer is found to have small bandgap and large ionization potential. Despite the low molecular weight, the polymer exhibited a high field-effect mobility after annealing. A high on/off ratio suggests the polymer possesses high stability against oxygen doping. The polymer device also showed good environmental stability. [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] Rate constant estimation for C1 to C4 alkyl and alkoxyl radical decompositionINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2006H. J. Curran Rate coefficients for alkyl and alkoxy radical decomposition are important in combustion, biological, and atmospheric processes. In this paper, rate constant expressions for C1C4 alkyl and alkoxy radicals decomposition via ,-scission are recommended based on the reverse, exothermic reaction, the addition of a hydrogen atom or an alkyl radical to an olefin or carbonyl species with the decomposition reaction calculated using microscopic reversibility. The rate expressions have been estimated based on a wide-range study of available experimental data. Rate coefficients for hydrogen atom and alkyl radical addition to an olefin show a strong temperature curvature. In addition, it is found that there is a correlation between the activation energy for addition and (i) the type of atom undergoing addition and (ii) whether this radical adds to the internal or terminal carbon atom of the olefin. Rate coefficients for alkoxy radical decomposition show a strong correlation to the ionization potential of the alkyl radical leaving group and on the enthalpy of reaction. It is shown that the activation energy for alkyl radical addition to a carbonyl species can be estimated as a function of the alkyl radical ionization potential and enthalpy of reaction. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 250,275, 2006 [source] Measurements of the kinetics of the OH + ,-pinene and OH + ,-pinene reactions at low pressureINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2002B. Chuong The rate constants for the OH + ,-pinene and OH + ,-pinene reactions have been measured in 5 Torr of He using discharge-flow systems coupled with resonance fluorescence and laser-induced fluorescence detection of the OH radical. At room temperature, the measured effective bimolecular rate constant for the OH + ,-pinene reaction was (6.08 ± 0.24) × 10,11 cm3 molecule,1 s,1. These results are in excellent agreement with previous absolute measurements of this rate constant, but are approximately 13% greater than the value currently recommended for atmospheric modeling. The measured effective bimolecular rate constant for the OH + ,-pinene reaction at room temperature was (7.72 ± 0.44) × 10,11 cm3 molecule,1 s,1, in excellent agreement with previous measurements and current recommendations. Above 300 K, the effective bimolecular rate constants for these reactions display a negative temperature dependence suggesting that OH addition dominates the reaction mechanisms under these conditions. This negative temperature dependence is larger than that observed at higher pressures. The measured rate constants for the OH + ,-pinene and OH + ,-pinene reactions are in good agreement with established reactivity trends relating the rate constant for OH + alkene reactions with the ionization potential of the alkene when ab initio calculated energies for the highest occupied molecular orbital are used as surrogates for the ionization potentials for ,- and ,-pinene. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 300,308, 2002 [source] Theoretical studies of some sulphonamides as corrosion inhibitors for mild steel in acidic mediumINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 14 2010Eno E. Ebenso Abstract Density functional theory (DFT) at the B3LYP/6-31G (d,p) and BP86/CEP-31G* basis set levels and ab initio calculations using the RHF/6-31G (d,p) methods were performed on four sulfonamides (namely sulfaacetamide (SAM), sulfapyridine (SPY), sulfamerazine (SMR), and sulfathiazole (STI)) used as corrosion inhibitors for mild steel in acidic medium to determine the relationship between molecular structure and their inhibition efficiencies (%IE). The order of inhibition efficiency obtained was SMR > SPY > STI > SAM which corresponded with the order of most of the calculated quantum chemical parameters namely EHOMO (highest occupied molecular orbital energy), ELUMO (lowest unoccupied molecular orbital energy), the energy gap (,E), the Mulliken charges on the C, O, N, S atoms, hardness (,), softness (S), polarizability (,), dipole moment (,), total energy change (,ET), electrophilicity (,), electron affinity (A), ionization potential (I), the absolute electronegativity (,), and the fraction of electrons transferred (,N). Quantitative structure activity relationship (QSAR) approach has been used and a correlation of the composite index of some of the quantum chemical parameters was performed to characterize the inhibition performance of the sulfonamides studied. The results showed that the %IE of the sulfonamides was closely related to some of the quantum chemical parameters but with varying degrees/order. The calculated %IE of the sulfonamides studied was found to be close to their experimental corrosion inhibition efficiencies. The experimental data obtained fits the Langmuir adsorption isotherm. The negative sign of the EHOMO values and other thermodynamic parameters obtained indicates that the data obtained supports physical adsorption mechanism. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Electronic structure and physicochemical properties of selected penicillinsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2007Catalina Soriano-Correa Abstract Traditionally, penicillins have been used as antibacterial agents due to their characteristics and widespread applications with few collateral effects, which have motivated several theoretical and experimental studies. Despite the latter, their mechanism of biological action has not been completely elucidated. We present a theoretical study at the Hartree,Fock and density functional theory (DFT) levels of theory of a selected group of penicillins such as the penicillin-G, amoxicillin, ampicillin, dicloxacillin, and carbenicillin molecules, to systematically determine the electron structure of full ,-lactam antibiotics. Our results allow us to analyze the electronic properties of the pharmacophore group, the aminoacyl side-chain, and the influence of the substituents (R and X) attached to the aminoacyl side-chain at 6, (in contrast with previous studies focused at the 3, substituents), and to corroborate the results of previous studies performed at the semiempirical level, solely on the ,-lactam ring of penicillins. Besides, several density descriptors are determined with the purpose of analyzing their link to the antibacterial activity of these penicillin compounds. Our results for the atomic charges (fitted to the electrostatic potential), the bond orders, and several global reactivity descriptors, such as the dipole moments, ionization potential, hardness, and the electrophilicity index, led us to characterize: the active sites, the effect of the electron-attracting substituent properties and their physicochemical features, which altogether, might be important to understand the biological activity of these type of molecules. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Systematic formulations for electronegativity and hardness and their atomic scales within density functional softness theoryINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2006Mihai V. Putz Abstract A unified Mulliken valence with Parr ground-state electronegativity picture is presented. It provides a useful analytical tool on which the absolute hardness as well ionization potential and electron affinity functionals are based. For all these chemical reactivity indices, systematic approximate density functionals are formulated within density functional softness theory and are applied to atomic systems. For the absolute hardness, a special relationship with the new electronegativity ansatz and a particular atomic trend paralleling the absolute electron affinity are established that should complement and augment the earlier finite-difference energetic approach. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] G-protein coupled receptors: SAR analyses of neurotransmitters and antagonistsJOURNAL OF CLINICAL PHARMACY & THERAPEUTICS, Issue 3 2004C. L. Kuo MS Summary Background:, From the deductive point of view, neurotransmitter receptors can be divided into categories such as cholinergic (muscarinic, nicotinic), adrenergic (, - and , -), dopaminergic, serotoninergic (5-HT1,5-HT5), and histaminergic (H1 and H2). Selective agonists and antagonists of each receptor subtype can have specific useful therapeutic applications. For understanding the molecular mechanisms of action, an inductive method of analysis is useful. Objective:, The aim of the present study is to examine the structure,activity relationships of agents acting on G-protein coupled receptors. Method:, Representative sets of G-PCR agonists and antagonists were identified from the literature and Medline [P.M. Walsh (2003) Physicians' desk reference; M.J. O'Neil (2001) The Merck index]. The molecular weight (MW), calculated logarithm of octanol/water partition coefficient (C log P) and molar refraction (CMR), dipole moment (DM), Elumo (the energy of the lowest unoccupied molecular orbital, a measure of the electron affinity of a molecule and its reactivity as an electrophile), Ehomo (the energy of the highest occupied molecular orbital, related to the ionization potential of a molecule, and its reactivity as a nucleophile), and the total number of hydrogen bonds (Hb) (donors and receptors), were chosen as molecular descriptors for SAR analyses. Results:, The data suggest that not only do neurotransmitters share common structural features but their receptors belong to the same ensemble of G-protein coupled receptor with seven to eight transmembrane domains with their resultant dipoles in an antiparallel configuration. Moreover, the analysis indicates that the receptor exists in a dynamic equilibrium between the closed state and the open state. The energy needed to open the closed state is provided by the hydrolysis of GTP. A composite 3-D parameter frame setting of all the neurotransmitter agonists and antagonists are presented using MW, Hb and , as independent variables. Conclusion:, It appears that all neurotransmitters examined in this study operate by a similar mechanism with the G-protein coupled receptors. [source] Structures and stability of lithium monosilicide clusters SiLin (n = 4,16): What is the maximum number, magic number, and core number for lithium coordination to silicon?JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 11 2008Ning He Abstract In the coordination, hypervalent and cluster chemistry, three important characteristic properties are the maximum coordination number, magic number, and core coordination number. Yet, few studies have considered these three numbers at the same time for an MLn cluster with n larger than 8. In this article, we systematically studied the three properties of SiLin (n = 4,16) clusters at the B3LYP/6-31G(d), B3LYP/6-311++G(2d), and CCSD(T)/6-311++G(3df)//B3LYP/6-311++G(2d) (for energy only) levels. Various isomeric forms with different symmetries were calculated. For each SiLin (n = 4,9), silicon cohesive energy (cE) from SiLin , Si + Lin reaction, vertical ionization potential (vIP), and vertical electron affinity (vEA) were obtained for the lowest-energy isomer. We found that the maximum Li-coordination number of Si is 9, which is the largest number among the known MLin clusters. All cE, vIP, and vEA values predicted that 6 is the magic Li-coordination number of Si. For small SiLin (n , 6) clusters, Li atoms favor direct coordination to Si, whereas for larger SiLin (n , 7) clusters, there is a core cluster that is surrounded by excessive Li atoms. The core Li-coordination number is 6 for SiLin (n = 7,8), 7 for SiLin (n = 9,10), 8 for SiLin (n = 11,15) and 9 for SiLin (n , 16). Through the calculations, we verified the relationship between the structure and stability of SiLin with the maximum coordination number, magic number, and core coordination number. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008 [source] Thermochemistry of cyclopentadienylidene (c-C5H4, C2v, 3B1), cyclopentadienyl radical (c-C5H5,, C2v, 2B1) and 1,3-cyclopentadiene (c-C5H6, C2v, 1A1): a theoretical study by the G2M(RCC,MP2) methodJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 3 2001Thanh Lam Nguyen Abstract The thermochemistry of c-C5H4 (3B1), c-C5H5, and c-C5H6 was investigated at the G2M(RCC,MP2) level. The heat of formation (,Hof,298), ionization potential (IP), electron affinity (EA) and proton affinity (PA) are respectively, 125.1, 204.4, 42.5 and 230.7,kcal,mol,1 for c-C5H4 (3B1), 63.5, 195.2, 44.9 and 197.2,kcal,mol,1 for c-C5H5, and 32.1, 199.9, 26.0 and 195.2,kcal,mol,1 for c-C5H6. The computed values for the last two molecules are in excellent agreement with available experimental data, with the errors of ±1 and ±2,kcal,mol,1 for the heat of formation and the other parameters, respectively. In addition, the heat of formation of c-C5H4,, is evaluated as 82.0,kcal,mol,1, about 10,kcal,mol,1 higher than the experimental value. This leads to the suggestion that the experimental ,Hof,298(c-C5H4,,) value needs to be re-examined. Copyright © 2001 John Wiley & Sons, Ltd. [source] Photophysical and electrochemical characterization of new poly(arylene vinylene) copolymers containing quinoline or bisquinoline segmentsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2009John A. Mikroyannidis Abstract Four new fluorescent conjugated vinylene-copolymers incorporating quinoline or bisquinoline segments along the backbone were synthesized by Heck coupling. Three of them were fluorenevinylene-copolymers and contained quinoline (PQFV, PQFVT) or bisquinoline segments (PBQFV). One of them (PBQPV) was phenylenevinylene-copolymer and contained bisquinoline segments. All the copolymers were soluble in common organic solvents and had relatively low glass transition temperature (Tg = 50,56 °C for fluorenevinylenes and Tg < 25 °C for phenylenevinylene). In THF solutions, the quinoline-containing copolymers showed absorption maxima at 411,420 nm while the bisquinoline-containing ones exhibited maxima at 357,361 nm. The emission maxima of solutions were 465,490 nm. The copolymers showed high quantum yields up to 64%. The films exhibited absorption and emission maxima in the range of 371,437 nm and 480,521 nm, respectively. All copolymers revealed reversible reduction with electron affinity of 2.66,3.53 eV and irreversible oxidation scans with ionization potential of 5.39,5.53 eV. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3370,3379, 2009 [source] Topological Electronegativity Index and Its Application , I. Ionization Potentials of Alkyl Groups and Alkyl HalidesMOLECULAR INFORMATICS, Issue 9 2007Chenzhong Cao Abstract A Topological Electronegativity Index (TEI) for alkyl group was developed, based on the bond adjacency matrix of the radical atom. Taking the radical atom and the adjacency atoms (or groups) as the vertices of molecular graph of the alkyl group, the bond adjacency matrix was constructed, in which the diagonal elements were assigned the Pauling electronegativity of the atom (or group), and the off-diagonal elements were assigned values 1 or 0. The off-diagonal elements represent the bond connections: that is when the two atoms (or groups) connect with each other, it is 1; otherwise is 0. From the matrix, the eigenvalues were obtained and its geometric mean value was considered as the TEI of an alkyl. The calculated TEI has good correlation with its experimental ionization potential. Further, the TEI was applied to correlate with the ionization potentials of alkyl halides and substituted ethenes, and to correlate with the Bond Dissociation Energies (BDEs) of the CiH bonds in alkanes. [source] Theoretical Elucidation of DPPH Radical-Scavenging Activity Difference of Antioxidant XanthonesMOLECULAR INFORMATICS, Issue 7 2005Hong-Fang Ji Abstract As naturally occurring polyphenols, xanthones are rather active in scavenging 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. By means of quantum chemical calculation, we reveal that the activity difference of xanthones can be elucidated by their different OH bond dissociation enthalpies (BDEs) and can be further explained in terms of electronic effect and intramolecular hydrogen bond effect of substituents. The unique structure of xanthones enables them to be promising antioxidants with advantages of rather low OH BDE and relatively high ionization potential. [source] QSAR of Human Steroid 5,-Reductase Inhibitors: Where are the differences between isoenzyme type 1 and 2?MOLECULAR INFORMATICS, Issue 6 2004Michael Abstract Quantitative Structure Activity Relationships have been established for inhibitors of human steroid 5,-reductase including 6-azasteroids and non-steroidal compounds. From the applied descriptors, those related to the molecular geometry, electronic properties, and the electrostatic surface were derived from semi-empirical AM1 calculations. A chemical reaction as part of the inhibitory action is indicated by the presence of the ionization potential in the descriptor space. Strong similarities between the variables for the prediction of the binding affinity to the type 1 and IC50 values for the type 2 isoform of the 5,-reductase were observed. The most pronounced differences in the linear regression QSAR equations were found for the descriptors accounting for the hydrogen-bonding interaction, suggesting a different hydrogen-bonding pattern in the binding pocket of both isoforms. Furthermore, the topological indices together with the surface related descriptors point towards a lower content of aromatic amino acids in the binding site of the type 2 isoenzyme. Consequences for the design of new inhibitors are discussed. [source] Dodging matrix effects in liquid chromatography tandem mass spectrometric assays,compilation of key learnings and perspectivesBIOMEDICAL CHROMATOGRAPHY, Issue 5 2009Nuggehally R. Srinivas Abstract Triple quad liquid chromatography mass spectrometric assays (LC/MS/MS) have revolutionized the analysis of drug(s)/metabolite(s) with exceptional speed, sensitivity and selectivity features. From inception to date, several new and innovative features have been regularly proposed by researchers to further enhance the value in the applicability of this analytical tool. However, owing to such compressed run times and scanty sample preparation procedures, LC/MS/MS assays that are not fully optimized generally have issues of matrix effects, where ionization potential is either suppressed or enhanced due to the presence of other materials (endogenous/exogenous) in the matrix. By definition, even co-medications, isomeric or isobaric impurities, and drug excipients used in dosing solutions could also potentially contribute to matrix effects. This article captures some of the interesting work carried out by researchers to understand and handle matrix effects. Additionally, it provides perspectives to effectively deal with matrix effects. Copyright © 2008 John Wiley & Sons, Ltd. [source] Studies on the Autoxidation of Aryl AlkenesCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 10 2006W. Ya. Abstract Autoxidation activity of substituted styrenes (aryl alkenes) and their product formation were studied in the temperature range of 65,125,°C using cumene or chlorobenzene as solvent. It was observed that higher reaction temperatures, inert solvent, electron donating substituents, and bulky sterical groups at ,-, ortho- and para- positions promoted radical formation of epoxides and led to C=C oxidative cleavage. In contrast, electron accepting substituents and using cumene as the solvent favored the formation of oligomeric peroxides. The relative activity of all investigated styrenes could be correlated to the linear free energy (LFE) relation and the ionization potential. For ,-substituted styrenes and ring substituted ,-methylstyrenes LFE correlation for the reactivity of aryl alkenes and formation of epoxides was found to depend on the polar and steric factors. A general pathway for product formation by autoxidation of aryl alkenes has been proposed. [source] Characteristics of Photoexcitations and Interfacial Energy Levels of Regioregular Poly(3-hexythiophene-2,5-diyl) on Gold,CHEMPHYSCHEM, Issue 13 2007Youngku Sohn Dr. Abstract We have studied characteristics of photoexcitations and interfacial electronic structures of regioregular poly(3-hexlythiophene-2,5-diyl) (P3HT) on gold using two-photon photoemission (2PPE) spectroscopy. The vacuum level threshold is decreased by 1.3 eV from that of bare gold, attributable to interface dipole effects. The 2PPE spectral width narrows as the film thickness increases. We tentatively understand that this is due to destabilization of long-lived localized polaron, attributed to strong interchain interactions. On the basis of the analysis of the 2PPE distribution as a function of photon energy and laser power, the polaron level is located at 3.1 eV below the vacuum level. Using this value and a polaron level of 1.75 eV above the HOMO, we indirectly estimate an ionization potential of 4.85 eV for P3HT. An increase in two-photon photoemission yield with increasing photon energy is attributed to an enhanced electron-hole pair dissociation yield at higher photo-excitation levels. The decrease in power law slope with increasing film thickness is understood by Langevin recombination kinetics and saturation of photoexcitations [source] Radii of Redox Components from Absolute Redox Potentials Compared with Covalent and Aqueous Ionic RadiiELECTROANALYSIS, Issue 9 2010Raji Heyrovska Abstract Aqueous standard potentials, referred to that of the SHE as zero, were recently shown to vary linearly with gaseous ionization potentials, with the absolute potential of SHE as the intercept. This enabled arriving at the absolute redox potentials of elements. Here, the distances between the oxidized and reduced forms in aqueous solutions have been evaluated. From the linear dependence of these distances on the covalent radii of atoms, the radii of the redox components have been obtained. The latter also vary linearly with the aqueous ionic radii estimated earlier from ion-water distances, and indicate the presence of aqueous molecular anions. [source] Variations in Hole Injection due to Fast and Slow Interfacial Traps in Polymer Light-Emitting Diodes with InterlayersADVANCED FUNCTIONAL MATERIALS, Issue 1 2010M. James Harding Abstract Detailed studies on the effect of placing a thin (10,nm) solution-processable interlayer between a light-emitting polymer (LEP) layer and a poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic)-acid-coated indium tin oxide anode is reported; particular attention is directed at the effects on the hole injection into three different LEPs. All three different interlayer polymers have low ionization potentials, which are similar to those of the LEPs, so the observed changes in hole injection are not due to variations in injection barrier height. It is instead shown that changes are due to variations in hole trapping at the injecting interface, which is responsible for varying the hole current by up to two orders of magnitude. Transient measurements show the presence of very fast interfacial traps, which fill the moment charge is injected from the anode. These can be considered as injection pathway dead-ends, effectively reducing the active contact surface area. This is followed by slower interfacial traps, which fill on timescales longer than the carrier transit time across the device, further reducing the total current. The interlayers may increase or decrease the trap densities depending on the particular LEP involved, indicating the dominant role of interfacial chain morphology in injection. Penetration of the interlayer into the LEP layer can also occur, resulting in additional changes in the bulk LEP transport properties. [source] Electronic Structure of Self-Assembled Monolayers on Au(111) Surfaces: The Impact of Backbone PolarizabilityADVANCED FUNCTIONAL MATERIALS, Issue 23 2009LinJun Wang Abstract Modifying metal electrodes with self-assembled monolayers (SAMs) has promising applications in organic and molecular electronics. The two key electronic parameters are the modification of the electrode work function because of SAM adsorption and the alignment of the SAM conducting states relative to the metal Fermi level. Through a comprehensive density-functional-theory study on a series of organic thiols self-assembled on Au(111), relationships between the electronic structure of the individual molecules (especially the backbone polarizability and its response to donor/acceptor substitutions) and the properties of the corresponding SAMs are described. The molecular backbone is found to significantly impacts the level alignment; for molecules with small ionization potentials, even Fermi-level pinning is observed. Nevertheless, independent of the backbone, polar head-group substitutions have no effect on the level alignment. For the work-function modification, the larger molecular dipole moments achieved when attaching donor/acceptor substituents to more polarizable backbones are largely compensated by increased depolarization in the SAMs. The main impact of the backbone on the work-function modification thus arises from its influence on the molecular orientation on the surface. This study provides a solid theoretical basis for the fundamental understanding of SAMs and significantly advances the understanding of structure,property relationships needed for the future development of functional organic interfaces. [source] Myth and Reality in the Attitude toward Valence-Bond (VB) Theory: Are Its ,Failures' Real?HELVETICA CHIMICA ACTA, Issue 4 2003Sason Shaik According to common wisdom propagated in textbooks and papers, valence-bond (VB) theory fails and makes predictions in contradiction with experiment. Four iconic ,failures' are: a) the wrong prediction of the ground state of the O2 molecule, b) the failure to predict the properties of cyclobutadiene (CBD) viz. those of benzene, c) the failure to predict the aromaticity/anti-aromaticity of molecular ions like C5H and C5H, C3H and C3H, C7H and C7H, etc; and d) the failure to predict that, e.g., CH4 has two different ionization potentials. This paper analyzes the origins of these ,failures' and shows that two of them (stated in a and d) are myths of unclear origins, while the other two originate in misuse of an oversimplified version of VB theory, i.e., simple resonance theory that merely enumerate resonance structures. It is demonstrated that, in each case, a properly used VB theory at a simple and portable level leads to correct predictions, as successful as those made by use of molecular-orbital (MO) theory. This notion of VB ,failure', which is traced back to the VB-MO rivalry, in the early days of quantum chemistry, should now be considered obsolete, unwarranted, and counterproductive. A modern chemist should know that there are two ways of describing electronic structure, which are not two contrasting theories, but rather two representations or two guises of the same reality. Their capabilities and insights into chemical problems are complementary, and the exclusion of any one of them undermines the intellectual heritage of chemistry. [source] Measurements of the kinetics of the OH + ,-pinene and OH + ,-pinene reactions at low pressureINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2002B. Chuong The rate constants for the OH + ,-pinene and OH + ,-pinene reactions have been measured in 5 Torr of He using discharge-flow systems coupled with resonance fluorescence and laser-induced fluorescence detection of the OH radical. At room temperature, the measured effective bimolecular rate constant for the OH + ,-pinene reaction was (6.08 ± 0.24) × 10,11 cm3 molecule,1 s,1. These results are in excellent agreement with previous absolute measurements of this rate constant, but are approximately 13% greater than the value currently recommended for atmospheric modeling. The measured effective bimolecular rate constant for the OH + ,-pinene reaction at room temperature was (7.72 ± 0.44) × 10,11 cm3 molecule,1 s,1, in excellent agreement with previous measurements and current recommendations. Above 300 K, the effective bimolecular rate constants for these reactions display a negative temperature dependence suggesting that OH addition dominates the reaction mechanisms under these conditions. This negative temperature dependence is larger than that observed at higher pressures. The measured rate constants for the OH + ,-pinene and OH + ,-pinene reactions are in good agreement with established reactivity trends relating the rate constant for OH + alkene reactions with the ionization potential of the alkene when ab initio calculated energies for the highest occupied molecular orbital are used as surrogates for the ionization potentials for ,- and ,-pinene. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 300,308, 2002 [source] Equivalent orbitals for multiconfigurational spin-tensor electron propagator method (MCSTEP): The vertical ionization potentials of B, NO, CF, and OFINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2008Dongxia Ma Abstract The multiconfigurational spin tensor electron propagator method (MCSTEP) was developed as an implementation of electron propagator/single particle Green's function methods for ionization potentials (IPs) and electron affinities (EAs). MCSTEP was specifically designed for open shell and highly correlated (nondynamically correlated) initial states. For computational efficiency the initial state used in MCSTEP is typically a small complete active space (CAS) multiconfigurational self-consistent field (MCSCF) state. If in a molecule there are some degenerate orbitals which are not fully or half occupied, usual MCSCF calculations will make these orbitals inequivalent, i.e., the occupied ones will be different from the nonoccupied ones, so that the degeneracy is broken. In this article, we use a state averaged MCSCF method to get equivalent orbitals for the initial state and import the integrals into the subsequent MCSTEP calculations. This gives, in general, more reliable MCSTEP vertical IPs. © 2008 Wiley Periodicals, Inc., 2008 [source] Density functional crystal orbital study of cyano-substituted poly(para -phenylene-vinylene) and poly(quinoxaline-vinylene)INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 8 2006F. Bartha Abstract We have calculated the optical and electronic properties of several conjugated organic polymers: poly(p -phenylene-vinylene) (PPV) and its derivatives. Cyano substitutions on the phenylene ring: poly(2,5-dicyano- p -phenylene-vinylene) (2,5-DCN-PPV) and on the vinylene linkage: poly(p -phenylene-7(,8)-(di)cyano-vinylene) are considered. In addition, poly(quinoxaline-vinylene) (PQV) is studied. The infinite isolated quasi-1D chains are treated with periodic boundary conditions, using atomic basis sets. In a comparative study of PPV, some issues regarding the selection of the functionals and basis sets are discussed and excitation energies derived from time-dependent and from ordinary methods are compared. It is concluded that for these polymers the calculations are informative at the B3LYP/6-31G** density functional theory (DFT) level. The absolute values might change with improved methods, but the similarity of the polymers suggests that the relative characterization is adequate. Band structures are communicated along with characteristics of the highest occupied and the lowest unoccupied crystal orbitals (HOCO and LUCO). Electron affinities, ionization potentials, valence and conduction bandwidths, and effective masses at the bandgap are given. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] | ||||||||||||||||||||||||||||