@article {2512, title = {Ab Initio Studies of Vacancy-Defected Fullerenes and Single-Walled Carbon Nanotubes}, journal = {Int. J. Quantum Chem.}, volume = {109}, number = {14}, year = {2009}, note = {ISI Document Delivery No.: 507VUTimes Cited: 1Cited Reference Count: 51Liu, Lei Vincent Tian, Wei Quan Wang, Yan Alexander6th Congress of the International-Society-for-Theoretical-Chemical-PhysicsJUL 19-24, 2008Vancouver, CANADAInt Soc Theoret Chem PhysSp. Iss. SI}, month = {Nov}, pages = {3441-3456}, type = {Proceedings Paper}, abstract = {

The structures, stabilities, and electronic properties of the single-vacancy-defected fullerenes, C-60 and C-70, and the single- and double-vacancy-defected single-walled carbon nanotubes (SWCNTs) were studied within density functional theory. The isomerization barriers for the single-vacancy-defected C,, on the triplet potential energy surface (PES) are lower than those on the singlet PES. The symmetric double-vacancy-defected (10,0) SWCNT is the most stable one among the models investigated. According to the analyses of frontier molecular orbitals (FMOs), nature bond orbitals, and local density of states, introduction of vacancy on the SWCNT decreases the band gap of semiconducting SWCNT, increases the band gap of conducting SWCNT, destructs the pi conjugation of the FMOs, and gives rise to enhanced chemical activity. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 109: 3441-3456, 2009

}, keywords = {BUCKMINSTERFULLERENE, C-60, COMPUTATIONS, CONDUCTANCE, density, EXCHANGE, FULLERENE, GENERALIZED GRADIENT APPROXIMATION, GROWTH, INHIBITION, OXIDES, single-walled carbon nanotube, vacancy defect}, isbn = {0020-7608}, url = {://000270884200026}, author = {Liu, L. V. and Tian, W. Q. and Y. A. Wang*} } @article {2475, title = {High Temperature End of the So-Called "Koga Line": Anomalies in Temperature Derivatives of Heat Capacities}, journal = {Journal of Physical Chemistry B}, volume = {113}, number = {17}, year = {2009}, note = {ISI Document Delivery No.: 438BCTimes Cited: 0Cited Reference Count: 24Koga, Yoshikata Westh, Peter Moriya, Yosuke Kawasaki, Koji Atake, Tooru}, month = {Apr}, pages = {5885-5890}, type = {Article}, abstract = {The so-called "Koga line" is a collection of the loci of anomalies in various third derivatives of the Gibbs function, G, in the temperature-mole fraction field for aqueous solutions of nonelectrolytes. This splits the H2O-rich region into two, in each of which the molecular organization and interactions-we call it mixing scheme-is qualitatively different. In this work, we attempt to locate the high temperature end of the Koga line. This is a particularly interesting range of the boundary, since its extrapolation to zero Solute concentration provides information on possible temperature induced changes in the properties of pure water. To this end, we determine semi-isobaric heat capacities of aqueous 2-butoxyethanol by adiabatic calorimetry up to a maximum of 95 degrees C. The corrections due to vaporization were not applied due to the lack of required vapor pressure and thermal expansivity data. Furthermore, we measured directly the isobaric heat capacities per molar volume for aqueous I-propanol as well as 2-butoxyethanol by differential scanning calorimetry up to 120 degrees C at 3 atm. We then took one more temperature derivative of the respective heat capacity data. The resulting third derivative quantities from the former data showed step-type anomalies, while those from the latter negative peak-type anomalies. The loci of these anomalous points seem to point to about 70 degrees C at infinite dilution.}, keywords = {25-DEGREES-C, AQUEOUS 2-BUTOXYETHANOL, density, FLUCTUATION, METHANOL, MIXING SCHEME, PARTIAL MOLAR VOLUMES, pressure, TRANSITION, WATER-RICH REGION}, isbn = {1520-6106}, url = {://000265529900029}, author = {Koga,Yoshikata and Westh, P. and Moriya, Y. and Kawasaki, K. and Atake, T.} } @article {2689, title = {Perturbative total energy evaluation in self-consistent field Iterations: Tests on molecular systems}, journal = {J. Chem. Phys.}, volume = {130}, number = {14}, year = {2009}, note = {ISI Document Delivery No.: 439HCTimes Cited: 0Cited Reference Count: 24Zhang, Yu Adam Wang, Yan Alexander}, month = {Apr}, pages = {144116}, type = {Article}, abstract = {

The corrected Hohenberg-Kohn-Sham and corrected Harris total energy functionals recently proposed [B. Zhou and Y. A. Wang, J. Chem. Phys. 128, 084101 (2008)] have been generalized to the Hartree-Fock method. We have tested the functionals on a few molecular systems and found them to be very useful in accelerating the convergence of the total energy during a self-consistent field process.

}, keywords = {AB-INITIO, CRC, density, density functional theory, ELECTRON-GAS, EXTREMAL PROPERTIES, HF calculations, iterative methods, PERTURBATION THEORY, SCF calculations, SOLIDS, total energy}, isbn = {0021-9606}, url = {://000265617200018}, author = {Zhang, Y. A. and Y. A. Wang*} } @article {2473, title = {Poly(oligo(ethylene glycol)acrylamide) Brushes by Surface Initiated Polymerization: Effect of Macromonomer Chain Length on Brush Growth and Protein Adsorption from Blood Plasma}, journal = {Langmuir}, volume = {25}, number = {6}, year = {2009}, note = {ISI Document Delivery No.: 418JRTimes Cited: 12Cited Reference Count: 45Kizhakkedathu, Jayachandran N. Janzen, Johan Le, Yevgeniya Kainthan, Rajesh K. Brooks, Donald E.}, month = {Mar}, pages = {3794-3801}, type = {Article}, abstract = {Three hydrolytically stable polyethyleneglycol (PEG)-based N-substituted acrylamide macromonomers, methoxypolyethyleneglycol (350) acrylamide (MPEG(350)Am) methoxypolyethyleneglycol (750) acrylamide(MPEG(750)Am) and methoxypolyethyleneglycol (2000)acrylamide (MPEG(2000)Am) with increasing PEG chain length were synthesized. Surface-initiated aqueous atom transfer radical polymerization (ATRP) using CuCl/1,1,4,7,10,10-hexamethyl triethylene tetramine (HMTETA) catalyst was utilized to generate dense polymer brushes from these monomers via an ester linker group on the surface of model polystyrene (PS) particles. The molecular weight, hydrodynamic thickness, and graft densities of the grafted polymer layers were controlled by changing the reaction parameters of monomer concentration, addition of Cu(II)Cl-2, and sodium chloride. The graft densities of surface-grafted brushes decreased with increasing PEG macromonomer chain length, 350 > 750 >> 2000, under similar experimental conditions. The molecular weight of grafts increased with increase in monomer concentration, and only selected conditions produced narrow distributed polymer chains. The molecular weight of grafted polymer chains differs significantly to those formed in solution. The hydrodynamic thicknesses of the grafted polymer layers were fitted to the Daoud and Cotton model (DCM) for brush height on spherical surfaces. The results show that the size of the pendent groups on the polymer chains has a profound effect on the hydrodynamic thickness of the brush for a given degree of polymerization. The new PEG-based surfaces show good protection against nonspecific protein adsorption from blood plasma compared to the bare surface. Protein adsorption decreased with increasing surface density of grafted polymer chains. Poly(MPEG(750)Am) brushes were more effective in preventing protein adsorption than poly(MPEG(350)Am) even at low graft densities, presumably due to the increase in PEG content in the grafted layer.}, keywords = {AQUEOUS ATRP, COPOLYMER BRUSHES, density, METHYL-METHACRYLATE, MODEL, N-DIMETHYLACRYLAMIDE), OLIGO(ETHYLENE GLYCOL) METHACRYLATE, PHOSPHORYLCHOLINE, POLY(N, POLYMERS, TRANSFER RADICAL POLYMERIZATION}, isbn = {0743-7463}, url = {://000264145000068}, author = {Kizhakkedathu, J. N. and Janzen, J. and Le, Y. and Kainthan, R. K. and Brooks, D. E.} } @article {2697, title = {Surface Modification of Polyvinyl Chloride Sheets via Growth of Hydrophilic Polymer Brushes}, journal = {Macromolecules}, volume = {42}, number = {9}, year = {2009}, note = {ISI Document Delivery No.: 441PNTimes Cited: 7Cited Reference Count: 65Zou, Yuquan Kizhakkedathu, Jayachandran N. Brooks, Donald E.}, month = {May}, pages = {3258-3268}, type = {Article}, abstract = {Poly(N,N-dimethylacrylamide) (PDMA) brushes were successfully grown from polyvinyl chloride (uPVC) sheets via well-controlled surface-initiated atom transfer radical polymerization (SI-ATRP). An ATRP initiator containing a chloropropionate moiety was chemically tethered onto the surface of PVC via it novel wet chemical modification. Negatively charged sulfate groups were introduced to facilitate polymerization. By incorporating a chemically cleavable group into the initiator, molecular weight, polydispersity and graft density of a series of PDMA brushes synthesized on the flat surface were unambiguously characterized for the first time by gel permeation chromatography. ATR-FTIR, contact angle, SEM and AFM were used to characterize the PDMA grafted surfaces. Reaction conditions Such as monomer concentration, reaction time, copper(II) concentration and salt additives were varied to systematically investigate their effects on molecular weight and graft density of the PDMA grafted from PVC. Molecular weights of grafted PDMA brushes varied from ca. 20 000 to 2 170 000 Da, while craft density ranged from 0.08 to 1.13 chains/nm(2). Polydispersity of grafted PDMA brushes was controlled between 1.20 and 1.60 by Cu(II) complex addition. Kinetic studies revealed that the surface initiation was a slow process and graft density increased during the reaction. The brush uniformity increased with increasing reaction time. Reinitiation of the obtained PDMA brushes was demonstrated, suggesting that the polymerization is "living". The successful growth of a PDMA-b-poly(N-isopropylacrylamide) (PNIPAM) copolymer brush was verified by GPC and AFM.}, keywords = {AQUEOUS ATRP, ATOMIC-FORCE MICROSCOPY, CARBON NANOTUBES, COPOLYMER BRUSHES, density, GLYCOL), GRAFT, PLASMA-PROTEIN ADSORPTION, POLY(ETHYLENE, SELF-ASSEMBLED MONOLAYERS, SERUM-ALBUMIN, TRANSFER RADICAL POLYMERIZATION}, isbn = {0024-9297}, url = {://000265781300007}, author = {Zou, Y. Q. and Kizhakkedathu, J. N. and Brooks, D. E.} } @article {2281, title = {Structure and vibrational assignment of the enol form of 1-chloro-1,1 difluoro-pentane-2,4-dione}, journal = {J. Mol. Struct.}, volume = {878}, number = {1-3}, year = {2008}, note = {ISI Document Delivery No.: 300CGTimes Cited: 0Cited Reference Count: 42Tayyari, Sayyed Faramarz Najafi, Atefeh Afzali, Raheleh Emamian, Saeedreza Wang, Yan Alexander}, month = {Apr}, pages = {10-21}, type = {Article}, abstract = {

Molecular structure of 1-chloro-1,1-difluoro-pentane-2,4-dione (monochlorodifluoro-acetylacetone, CDFAA) has been investigated by means of ab initio and Density Functional Theory (DFT) calculations and the results were compared with those of 1,1,1-trifluoropentane-2,4-dione (trifluoro-acetylacetone, TFAA). The harmonic vibrational frequencies of the two most stable cis-enol forms were calculated at the 133LYP level of theory using 6-3 1 G** and 6-311 ++G** basis sets. We also calculated the anharmonic frequencies at the B3LYP/6-31G** level of theory for these two stable cis-enol isomers. The calculated frequencies and the Raman and IR intensities were compared with the experimental results. The energy difference between the two stable cis-enol forms, calculated at the MP2/6-31G** level, is only 3.42 U/mol. The observed vibrational frequencies and intensities in the gas phase are in excellent agreement with the corresponding values calculated for the two most stable conformers. However, the observed IR and Raman frequencies also indicate coexisting of both tautomers in the liquid phase and in solution. According to the theoretical calculations, at the B3LYP/6-31 1++G** level, the hydrogen bond strength for the most stable conformer is 54.45 U/mol, about 2.4 kJ/mol less than that of the corresponding conformer of TFAA. These results are in agreement with the obtained experimental data. (C) 2007 Elsevier B.V. All rights reserved.

}, keywords = {1-chloro-1, 1-difluoro-pentane-2, 4-dione, AB-INITIO, anharmonicity, BETA-DIKETONES, density, ELECTRON-DIFFRACTION, ENERGY, EQUILIBRIUM, functional theory, HEXAFLUORO-ACETYLACETONE, intramolecular hydrogen bond, MALONALDEHYDE, MOLECULAR-STRUCTURE, TAUTOMERISM, vibrational spectra}, isbn = {0022-2860}, url = {://000255801300002}, author = {S. F. Tayyari* and Najafi, A. and Afzali, R. and Emamian, S. and Wang, Y. A.} } @article {1467, title = {Chemical reaction of nitric oxides with the 5-1DB defect of the single-walled carbon nanotube}, journal = {J. Phys. Chem. B}, volume = {110}, number = {5}, year = {2006}, note = {ISI Document Delivery No.: 011QXTimes Cited: 15Cited Reference Count: 39}, month = {Feb}, pages = {1999-2005}, type = {Article}, abstract = {

In this work, we applied a two-layered ONIOM (B3LYP/6-31G(d):UFF) method to study the reaction of nitric oxides with a 5-1DB defect on the sidewall of the single-walled carbon nanotube (SWCNT). We have chosen a suitable ONIOM model for the calculation of the SWCNT based on the analyses of the frontier molecular orbitals,, local density of states, and natural bond orbitals. Our calculations clearly indicate that the 5-1DB defect is the chemically active center of the SWCNT. In the reaction of nitric oxides with the defected SWCNT, the 5-1DB defect site can capture a nitrogen atom from nitric oxides, yielding the N-substitutionally doped SWCNT. We have explored the reaction pathway in detail. Our work verifies the chemical reactivity of the 5-1DB defects of the SWCNTs, indicates that the 5-1DB defect is a possible site for the functionalization of the SWCNTs, and demonstrates a possible way to fabricate position controllable substitutionally doped SWCNTs with a low doping concentration under mild conditions via some simple chemical reactions.

}, keywords = {AB-INITIO, BORON, chemisorption, density, DOPED CARBON, MOLECULAR-MECHANICS, NITROGEN, ONIOM, OPTIMIZATION, sensors}, isbn = {1520-6106}, url = {://000235284300009}, author = {Liu, L. V. and Tian, W. Q. and Y. A. Wang*} } @article {1338, title = {Salts of the cobalt(I) complexes [Co(CO)(5)](+) and[Co(CO)(2)(NO)(2)](+) and the Lewis acid-base adduct [CO2(CO)(7)CO-B(CF3)(3)]}, journal = {Chemistry-a European Journal}, volume = {12}, number = {32}, year = {2006}, note = {ISI Document Delivery No.: 110YZTimes Cited: 4Cited Reference Count: 60Bernhardt, Eduard Finze, Maik Willner, Helge Lehmann, Christian W. Aubke, Friedhelm}, month = {Nov}, pages = {8276-8283}, type = {Article}, abstract = {The reaction of [Co-2(CO)(8)] with (CF3)(3)BCO in hexane leads to the Lewis acid-base adduct [CO2(CO)(7)COB(CF3)(3)] in high yield. When the reaction is performed in anhydrous HF solution [Co(CO)(5)][(CF3)(3)BF] is isolated. The product contains the first example of a homoleptic metal pentacarbonyl cation with 18 valence electrons and a trigonal-bipyramidal structure. Treatment of [Co-2(CO)(8)] or [Co(CO)(3)NO] with NO+ salts of weakly coordinating anions results in mixed crystals containing the [Co(CO)(5)](+)/[Co(CO)(2)(NO)(2)](+) ions or pure novel [Co(CO)(2)(NO)(2)](+) salts, respectively. This is a promising route to other new metal carbonyl nitrosyl cations or even homoleptic metal nitrosyl cations. All compounds were characterized by vibrational spectroscopy and by single-crystal X-ray diffraction.}, keywords = {ALUMINUM HALIDES, ANIONS, carbonyl ligands, cobalt, density, density functional calculations, DICOBALT OCTACARBONYL, EXCHANGE, LIGANDS, METAL-CARBONYL CATIONS, NITRIC-OXIDE, NITROSYL, SOLID-STATE, SPECTROSCOPIC PROPERTIES, vibrational spectroscopy, VIBRATIONAL-SPECTRA}, isbn = {0947-6539}, url = {://000242418600008}, author = {Bernhardt, E. and Finze, M. and Willner, H. and Lehmann, C. W. and Aubke, F.} } @article {1169, title = {Intermolecular activation of hydrocarbon C-H bonds initiated by the tungsten hydrocarbyl hydrido complexes Cp*W(NO)(R)(H)(PMe3) (R = alkyl, aryl)}, journal = {Organometallics}, volume = {24}, number = {4}, year = {2005}, note = {ISI Document Delivery No.: 896HITimes Cited: 5Cited Reference Count: 32}, month = {Feb}, pages = {638-649}, type = {Article}, abstract = {trans-CP*W(NO)(CH2EMe3)(H)(PMe3) (E = C, Si) complexes can be prepared by the hydrogenation at 1 atm of the appropriate Cp*W(NO)(CH2EMe3)(2) precursor in the presence of a slight excess of PMe3. (Our designation of a particular geometrical isomer as cis or trans in this family of complexes indicates the relative positions of the hydrocarbyl and the hydrido ligands in the base of a four-legged piano-stool molecular structure.) The use of D-2 in place of H-2 during these syntheses affords the corresponding trans-Cp*W(NO)(CH2EMe3)(D)(PMe3) (E = C, Si) complexes. The cis-Cp*W(NO)(CH2EMe3)(H)(PMe3) isomers are obtainable by C-H bond-activation reactions of the trans precursors. Thus, activation of SiMe4 by trans-Cp*W(NO)(CH2CMe3)(H)(PMe3) under ambient conditions produces cis-Cp*W(NO)(CH2SiMe3)(H)(PMe3). Similarly, activations of C6H6 and C6D6 at 20-27 degreesC by the trans-Cp*W(NO)(CH2EMe3)(H)(PMe3) complexes produce cis-Cp*W(NO)(C6H5)(H)(PMe3) and cisCp*W(NO)(C6D5)(D)(PMe3), respectively, and the solid-state molecular structure of the latter complex has been established by a single-crystal X-ray crystallographic analysis. Kinetic, mechanistic, and theoretical investigations of these benzene C-H activation processes are consistent with initial trans to cis isomerization of the reactants followed by intramolecular reductive elimination of EMe4 to form the 16-electron Cp*W(NO)(PMe3) intermediate. Subsequent oxidative addition of the incoming benzene substrate to this coordinatively unsaturated intermediate produces the final cis hydrido phenyl complex. These single C-H activation processes are the requisite first steps in the development of these organometallic complexes as catalysts for the selective functionalization of hydrocarbons. All new complexes have been characterized by conventional spectroscopic methods.}, keywords = {CALCULATIONS, density, EFFECTIVE CORE POTENTIALS, MOLECULAR, MOLYBDENUM, ORGANOMETALLIC NITROSYL CHEMISTRY, REACTIVITY}, isbn = {0276-7333}, url = {://000226924800024}, author = {Lee, K. and Legzdins,Peter and Pamplin, C. B. and Patrick, B. O. and Wada, K.} } @inbook {654, title = {Synthesis of poly(N,N-dimethylacrylamide) brushes from functionalized latex surfaces by aqueous atom transfer radical polymerization}, booktitle = {Advances in Controlled/Living Radical Polymerization}, series = {Acs Symposium Series}, volume = {854}, year = {2003}, note = {ISI Document Delivery No.: BW85KTimes Cited: 7Cited Reference Count: 30Proceedings Paper224th National Meeting of the American-Chemical-SocietyAUG 17-22, 2002BOSTON, MASSACHUSETTSAmer Chem Soc1155 SIXTEENTH ST NW, WASHINGTON, DC 20036 USA}, pages = {316-330}, publisher = {Amer Chemical Soc}, organization = {Amer Chemical Soc}, address = {Washington}, abstract = {Negatively charged, ATRP initiator functionalized polystyrene latexes were synthesized and N,N-dimethylacrylamide was polymerized from their surfaces by aqueous ATRP using several catalyst combinations. Very high grafting densities and molecular weights were achieved with good polydispersities. The brushes exhibited a strong repulsive force that increased with molecular weight in atomic force microscopy measurements. Hydrodynamic thicknesses were consistent with theory. Polymerization from these surfaces is very different from ATRP in solution and depends on monomer concentration in solution, type of catalyst, and surface initiator concentration. The observations were explained with an electrostatic model of the surface region that predicts an increase in the local concentration of Cu(I) and Cu(II) catalyst complexes.}, keywords = {ADSORPTION, BLOCK-COPOLYMERS, density, FORCE MICROSCOPE, INITIATED POLYMERIZATIONS, LAYER, MEDIA, POLYMERS, SELF-ASSEMBLED MONOLAYERS}, isbn = {0097-61560-8412-3854-5}, url = {://000183406500022}, author = {Kizhakkedathu, J. N. and Goodman, D. and Brooks, D. E.}, editor = {Matyjaszewski, K.} } @article {629, title = {Toward binary nitrosyls: Distinctly bent Fe-N-O linkages in base-stabilized Fe(NO)(3)(+) complexes}, journal = {Journal of the American Chemical Society}, volume = {125}, number = {42}, year = {2003}, note = {ISI Document Delivery No.: 733FYTimes Cited: 15Cited Reference Count: 50}, month = {Oct}, pages = {12935-12944}, type = {Article}, abstract = {Air- and moisture-sensitive Fe(NO)(3)(eta(1)-PF6) (1) may be conveniently prepared by treating Fe(NO)(3)Cl with 1 equiv of [Ag][PF6] in CH2Cl2 or by reacting [NO][PF6] with excess iron filings in MeNO2. Complex 1 is thermally sensitive both as a solid and in solutions, and is best handled below -20 degreesC. To isolate 1 reproducibly from MeNO2 solutions it is necessary to remove all traces of propionitrile, which often occurs as an impurity in MeNO2, because it reacts with Lewis-acidic 1 to form [Fe(NO)(3)(EtCN)][PF6] (2). If trace H2O is present during the synthesis of 1, some of the PF6- is converted to PO2F2-, which is sufficiently Lewis basic that it captures two Fe(NO)(3)(+) fragments and forms [(ON)(3)Fe(mu-PO2F2)Fe(NO)(3)]-[PF6] (3). Finally, Fe(NO)(3)(eta(1)-BF4) (4) can be obtained as a green microcrystalline powder by employing the same synthetic methodologies used to prepare 1. The new complexes 1-4 have been characterized by conventional spectroscopic methods, and the solid-state molecular structures of 2, 3, and 4 and their parent compound, Fe(NO)(3)Cl, have been established by X-ray diffraction methods. The iron centers in the Fe(NO)(3) fragments in all these structures exhibit approximately tetrahedral coordination geometries, and the Fe-N-O linkages are distinctly nonlinear with bond angles in the range of 159 to 169degrees. DFT calculations on Fe(NO)(3)(eta(1)-BF4) (4) confirm that its bent Fe-N-O links have an electronic origin and need not be attributed to other factors, such as packing forces in the crystal. Interestingly, the bending of the NO ligands results in an increase in the energy of the HOMO, relative to the linear case, but at the same time causes a decrease in energy of the HOMO-1 and the HOMO-2 molecular orbitals. This more than compensates for the higher energy of the HOMO, resulting in a lower energy structure.}, keywords = {basis set, CALCULATIONS, COORDINATION, CRYSTAL-STRUCTURE, density, impurities, MOLECULAR, NITROMETHANE, PURIFICATION, REFINEMENT, TETRANITROSYLCHROMIUM CR(NO)4}, isbn = {0002-7863}, url = {://000185990300054}, author = {Hayton, T. W. and McNeil, W. S. and Patrick, B. O. and Legzdins,Peter} } @article {470, title = {Theoretical X-ray photoelectron and Auger electron spectra of polymers by density functional theory calculations using model dimers}, journal = {Journal of Molecular Structure-Theochem}, volume = {619}, year = {2002}, note = {ISI Document Delivery No.: 624QZTimes Cited: 2Cited Reference Count: 21}, month = {Dec}, pages = {241-247}, type = {Article}, abstract = {We present theoretical X-ray photoelectron spectra (XPS) and Auger electron spectra (AES) for polymers by density functional theory (DFT) calculations with the Slater{\textquoteright}s transition-state concept. The simulated XPS and AES of three polymers [poly(ethylene) (PE), poly(cis-butadiene) (PcBD), and poly(styrene) (PS)] by DFT calculations using model molecules are in good accordance with the experimental ones. The combined analysis of AES and XPS enable us to clarify the electronic structure of single and double,excitation for polymers from the theoretical viewpoint. (C) 2002 Elsevier Science B.V. All rights reserved.}, keywords = {APPROXIMATION, Auger electron spectra, density, ENERGY, functional theory, LINE-SHAPES, molecular orbital calculation, polymer, SIO2, X-ray photoelectron spectra}, isbn = {0166-1280}, url = {://000179773300019}, author = {Otsuka, T. and Koizumi, S. and Endo, K. and Chong, D. P.} } @article {5207, title = {Effects of pressure and temperature on the solubility of monosodium L-glutamate monohydrate in water}, journal = {High Pressure Research}, volume = {21}, number = {2}, year = {2001}, note = {ISI Document Delivery No.: 572UGTimes Cited: 4Cited Reference Count: 21}, pages = {93-104}, type = {Article}, abstract = {The solubility of monosodium L-glutamate monohydrate (MSG.H2O) in water was measured at pressures in the range of 0.10-300 MPa and 298.15 K. The density of MSG solution at high concentrations and heat of solution at saturated concentration were also measured at atmospheric pressure. The solubility, m,, increased with increasing pressure and the pressure coefficient, theta(p) [equivalent to(partial derivative ln m(s)/partial derivativep)(T)], at 0. 10 MPa was (2.0 +/- 0.1) x 10(-10) Pa-1. It agrees well with (2.1 +/- 0.2) x 10(-10) Pa-1 thermodynamically estimated using the partial molar volume, the activity coefficient of the solute in solution, and the molar volume of the crystal. The excellent agreement at 0.10 MPa gives us confidence in the solubility data at higher pressures. The heat of solution data and other pertinent values were used to calculate the temperature coefficient of solubility, theta(T) [equivalent to(partial derivative ln ms/partial derivative(1/T))(p)], by a thermodynamic equality. The resulting theta(T) compares well with the data directly measured by Ogawa.}, keywords = {25-DEGREES-C, amino acids, CRYSTAL, density, heat of, HIGH-PRESSURE, molar volume, SOLUBILITY, SOLUTION}, isbn = {0895-7959}, url = {://000176792900003}, author = {Suzuki, Y. and Matsuo, H. and Koga,Yoshikata and Mukae, K. and Kawakita, T. and Sawamura, S.} } @article {5027, title = {Pressure-induced change in orientational order of solutes in liquid crystals}, journal = {Chemical Physics Letters}, volume = {337}, number = {4-6}, year = {2001}, note = {ISI Document Delivery No.: 420BPTimes Cited: 1Cited Reference Count: 20}, month = {Apr}, pages = {248-254}, type = {Article}, abstract = {The H-1 and H-1 NMR spectroscopy of the nematic liquid crystal ZLI 1132 containing small amounts of the solutes 1,3,5- trichlorobenzene. p-dichlorobenzene and acetone was investigated as a function of the pressure of a mixture of molecular hydrogen and deuterium gases above the sample. A general increase of solute orientational order with pressure was observed. Differences in behavior of the orientational order of the hydrogens compared to the other solutes are discussed. (C) 2001 Elsevier Science B.V. All rights reserved.}, keywords = {COMPUTER-SIMULATION, density, MAGNETIC-RESONANCE, MOLECULES, NEMATIC PHASE, NMR, SOLVENTS, TEMPERATURE-DEPENDENCE}, isbn = {0009-2614}, url = {://000167984300004}, author = {Burnell, E. E. and de Lange, C. A. and Gaemers, S.} } @article {4208, title = {Analyte-additive interactions in nonaqueous capillary electrophoresis: a critical review}, journal = {Trac-Trends in Analytical Chemistry}, volume = {17}, number = {7}, year = {1998}, note = {ISI Document Delivery No.: 107HPTimes Cited: 54Cited Reference Count: 40}, month = {Aug}, pages = {424-434}, type = {Review}, abstract = {This article reviews the recent developments in nonaqueous capillary electrophoresis and discusses the effect of the solvent on analyte-additive interactions. When nonaqueous solvents are used, solvophobic interactions are generally weaker than those in water; therefore, those additives that can change the analyte mobility through electrostatic or donor-acceptor interactions should be further explored. (C) 1998 Elsevier Science B.V. All rights reserved.}, keywords = {ANIONS, CHIRAL SEPARATION, cohesion energy, density, dielectric constant, electron donor-acceptor interaction, FORMAMIDE, ION, MEDIA, nonaqueous capillary electrophoresis, SEPARATION SELECTIVITY, solvent effect, SOLVENTS, SURFACTANTS, WATER, ZONE ELECTROPHORESIS}, isbn = {0165-9936}, url = {://000075202300022}, author = {Bowser, M. T. and Kranack, A. R. and Chen, D. D. Y.} } @article {4230, title = {Density-functional calculation of the inner-shell spectra for two stable enol tautomers: acetylacetone and malonaldehyde}, journal = {Journal of Electron Spectroscopy and Related Phenomena}, volume = {94}, number = {1-2}, year = {1998}, note = {ISI Document Delivery No.: 100GBTimes Cited: 10Cited Reference Count: 25}, month = {Jun}, pages = {181-185}, type = {Article}, abstract = {In this paper we report results from our theoretical studies on two P-diketones which exist as stable enol tautomers: acetylacetone and malonaldehyde. We found that density functional theory (DFT) with Becke{\textquoteright}s exchange functional and Perdew{\textquoteright}s correlation functional can accurately predict the core-electron binding energies (CEBEs) of both molecules. The oxygen 1s {\textendash}> pi* inner-shell excitation spectra (ISES) of both tautomers have also been studied using our DFT procedure. The CEBEs for the corresponding carbons and oxygens of the C=O and C-OH groups of malonaldehyde are larger than those of acetylacetone, The first term values corresponding to a core-hole on the carbonyl oxygen were found to be larger than those with a core-hole on the enol oxygen. The observation indicates that the effect of a core-hole in the proximity of pi*: orbital has a stronger effect on increasing the electron affinity of the core-ionized cation. (C) 1998 Elsevier Science B.V. All rights reserved.}, keywords = {APPROXIMATION, ATOMS, core electron binding energies, density, ELECTRON BINDING-ENERGIES, enols of acetylacetone and malonaldehyde, EXCHANGE, functional theory, HYDROGEN, INNER-SHELL EXCITATION, SPECTROSCOPY}, isbn = {0368-2048}, url = {://000074806800018}, author = {Chong, D. P. and Hu, C. H.} } @article {4442, title = {An investigation of dynamical density functional theory for solvation in simple mixtures}, journal = {Journal of Chemical Physics}, volume = {108}, number = {15}, year = {1998}, note = {ISI Document Delivery No.: ZH114Times Cited: 27Cited Reference Count: 48}, month = {Apr}, pages = {6378-6386}, type = {Article}, abstract = {Linear and nonlinear versions of time dependent density functional theory are solved for a single solute particle in a simple binary solvent. All particles interact with Lennard-Jones potentials. The theoretical results are compared with molecular dynamics calculations. It is shown that the nonlinear theory is necessary in order to obtain a good quantitative description of selective solvation dynamics. The linear theory is only of qualitative value. Also, attention is drawn to a previously little appreciated problem which arises when one attempts to compare time dependent density functional theory with computer simulation or experimental results. The difficulty involves matching the theoretical and absolute time scales and is discussed in detail in this paper. (C) 1998 American Institute of Physics. [S0021-9606(98)50615-0].}, keywords = {BINARY DIPOLAR LIQUIDS, COLLECTIVE ORIENTATIONAL RELAXATION, density, DIELECTRIC-RELAXATION, ELECTROLYTE-SOLUTIONS, ION SOLVATION, MOLECULAR THEORY, NONPOLAR SOLVATION, NUMBER, POLAR, SURROGATE HAMILTONIAN DESCRIPTION}, isbn = {0021-9606}, url = {://000073073700034}, author = {Yoshimori, A. and Day, T. J. F. and Patey, G. N.} } @article {3917, title = {Accurate density functional calculation of core electron binding energies .5. Application to nitriles. Model molecules for polyacrylonitrile revisited}, journal = {Journal of Electron Spectroscopy and Related Phenomena}, volume = {83}, number = {2-3}, year = {1997}, note = {ISI Document Delivery No.: XC597Times Cited: 24Cited Reference Count: 30}, month = {Feb}, pages = {227-234}, type = {Article}, abstract = {A recent procedure for computing accurate core electron binding energies (CEBEs) via density functional theory (DFT) is applied to acetonitrile, propionitrile, 2-cyanopropane, acrylonitrile, methacrylonitrile and the 2-methylglutaronitrile conformer of lowest energy, The first three systems have been studied in the past as model compounds to interpret the XPS spectrum of polyacrylonitrile (PAN) using post-Hartree-Fock finite-difference calculations, in order to solve a controversy in the assignment of chemically shifted atoms in the C 1s region, This assignment is revisited with the unrestricted generalized transition-state model and a combined functional of Becke{\textquoteright}s 1988 exchange with Perdew{\textquoteright}s 1986 correlation. Using Dunning{\textquoteright}s correlation-consistent polarized valence triple zeta basis sets with scaling improvements, we obtain predicted CEBEs for gasphase acetonitrile, propionitrile and acrylonitrile in remarkable agreement with experiment (average absolute deviation 0.09 eV). The CEBEs of these systems confirm the overall trends of the previous attributions of their respective gas-phase XPS spectrum, except in the case of propionitrile. These results, as well as those on 2-cyanopropane, methacrylonitrile and 2-methylglutaronitrile, bring some additional information on the extrapolation of the results to the assignment of the C 1s contributions of polyacrylonitrile. (C) 1997 Elsevier Science B.V.}, keywords = {APPROXIMATION, BASIS-SETS, computation, CORE LEVELS, density, functional theory, GAS-PHASE, NITRILES, POLYACRYLONITRILE, SPECTROSCOPY, X-ray photoelectron spectroscopy, XPS}, isbn = {0368-2048}, url = {://A1997XC59700014}, author = {Bureau, C. and Chong, D. P. and Lecayon, G. and Delhalle, J.} } @article {3723, title = {Normalized fluctuations, H2O vs n-hexane: Site-correlated percolation}, journal = {Journal of Chemical Physics}, volume = {105}, number = {5}, year = {1996}, note = {ISI Document Delivery No.: UZ525Times Cited: 20Cited Reference Count: 49}, month = {Aug}, pages = {2028-2033}, type = {Article}, abstract = {Entropy, volume and the cross fluctuations were normalized to the average volume of a coarse grain with a fixed number of molecules, within which the local and instantaneous value of interest is evaluated. Comparisons were made between liquid H2O and n-hexane in the range from -10 degrees C to 120 degrees C and from 0.1 MPa to 500 MPa. The difference between H2O and n-hexane in temperature and pressure dependencies of these normalized fluctuations was explained in terms of the site-correlated percolation theory for H2O. In particular, the temperature increase was confirmed to reduce the hydrogen bond probability, while the pressure appeared to have little effect on the hydrogen bond probability. According to the Le Chatelier principle, however, the putative formation of {\textquoteright}{\textquoteright}ice-like{\textquoteright}{\textquoteright} patches at low temperatures due to the site-correlated percolation requirement is retarded by pressure increases. Thus, only in the limited region of low pressure (<300 MPa) and temperature (<60 degrees C), the fluctuating ice-like patches are considered to persist. (C) 1996 American Institute of Physics.}, keywords = {2 KINDS, AQUEOUS 2-BUTOXYETHANOL, density, H-BONDS, HEAVY-WATER, LIQUID WATER, mixing, MOLECULAR-DYNAMICS, pressure, SCHEME, TEMPERATURES}, isbn = {0021-9606}, url = {://A1996UZ52500029}, author = {Koga,Yoshikata and Westh, P. and Sawamura, S. and Taniguchi, Y.} } @article {3503, title = {Momentum Profiles for Open-Shell Molecules: Studies of the HOMO{\textquoteright}s of NO, O2, and NO2 by Electron Momentum Spectroscopy and SCF, Post-Hartree-Fock and DFT Calculations}, journal = {Chem. Phys.}, volume = {201}, number = {1}, year = {1995}, note = {ISI Document Delivery No.: TH205Times Cited: 29Cited Reference Count: 74}, month = {Dec}, pages = {1-21}, type = {Article}, abstract = {

Measurements of the outermost valence electron orbital momentum profiles of the open shell molecules NO, O-2 and NO2 have been obtained using electron momentum spectroscopy (EMS). The presently reported experimental momentum profiles of NO and O-2 display much improved statistics compared with previously published EMS results while the data for the HOMO of NO, is the first reported. In the case of NO, the present measurements are considerably different from previous results and these differences appear to be due to the presence of NO2 impurities in the previous work. The EMS measurements provide a stringent test of basis set effects and the quality of ab initio methods in the description of these open shell systems. The experimental momentum profiles have been compared with theoretical spherically averaged momentum profiles from several basis sets calculated at the level of the target Hartree-Fock approximation (THFA) with a range of basis sets using both unrestricted Hartree-Fock (UHF) and restricted open shell Hartree-Fock (ROHF) methods. Various configuration interaction calculations such as multi-reference singles and doubles configuration interaction (MRSD-CI), averaged coupled pair functional (ACPF) and quasi-degenerate variational perturbation theory (QDVPT) calculations of the full ion-neutral overlap amplitude have also been compared to experiment to investigate the effects of electron correlation and relaxation. The experimental momentum profiles have further been compared to calculations at the level of the target Kohn-Sham approximation (TKSA) using density functional theory (DFT) with the local density approximation and also with gradient corrected exchange-correlation potentials. In addition to momentum profiles, other electronic properties such as total energies, dipole moments, quadrupole moments and values of the electronic spatial extent have been calculated by the various theoretical methods and compared to experimental values.

}, keywords = {CORRELATED WAVEFUNCTIONS, CORRELATION ENERGIES, density, DIPOLE-MOMENT, EXCHANGE-ENERGY, GAUSSIAN-BASIS SETS, NITRIC-OXIDE, VALENCE ORBITALS, VARIATIONAL PERTURBATION-THEORY, WAVE-FUNCTIONS}, isbn = {0301-0104}, url = {://A1995TH20500001}, author = {Rolke, J. and Cann, N. and Zheng, Y. and Hollebone, B. P. and C. E. Brion* and Wang, Y. A. and Davidson, E. R.} }