ChemPhysChem

Cover image for Vol. 6 Issue 3

March 11, 2005

Volume 6, Issue 3

Pages 381–562

    1. Cover Picture: Wetting of Surfactant Solutions by Alkanes (ChemPhysChem 3/2005) (page 381)

      Katherine M. Wilkinson, Colin D. Bain, Hiroki Matsubara and Makoto Aratono

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200590000

      The cover picture shows a cut-away section of an oil droplet on a surfactant solution, in which a lens of oil is in equilibrium with a mixed monolayer of surfactant and oil. The background is a Brewster angle micrograph of a drop of hexadecane on a 1.2 mM solution of dodecyltrimethylammonium bromide (DTAB), just above the wetting transition. In their article on page 547, Wilkinson et al. show that first-order wetting transitions in alkanes on surfactant solutions are a general, but not universal, phenomenon.

    2. Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H2O Complexes with Oxidants (pages 392–412)

      Petr G. Sennikov, Stanislav K. Ignatov and Otto Schrems

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400405

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      Water in the air: The activity of oxidizing species in the atmosphere can be extremely dependent on the complexes that they form with water molecules, water clusters, or ice particles. The authors summarize what is known, from both experimental and theoretical studies, on the structure and properties of such complexes (an adsorption complex of ozone at an ice surface is shown in the picture).

    3. Molecular Rotation as a Tool for Exploring Specific Solute–Solvent Interactions (pages 413–418)

      G. B. Dutt

      Version of Record online: 10 FEB 2005 | DOI: 10.1002/cphc.200400337

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      Solute–solvent interactions play an important role in determining the physicochemical properties of liquids and solutions. As a consequence, understanding these interactions has been one of the long-standing problems in physical chemistry. This Minireview describes some of the ongoing efforts towards attaining this goal. A typical solute–solvent complex is formed due to hydrogen-bonding interactions between two carbonyl and secondary amino groups of an organic solute and two ethanol molecules (see graphic).

    4. Femtochemistry of Inter- and Intramolecular Hydrogen Bonds (pages 419–423)

      Abderrazzak Douhal, Mikel Sanz, Laura Tormo and Juan Angel Organero

      Version of Record online: 18 FEB 2005 | DOI: 10.1002/cphc.200400375

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      Femtosecond studies of 3-hydroxyflavone complexed to a hydrogen-bonding solvent show that competitive inter- and intramolecular proton-transfer reactions are responsible for the production of (A) anionic and (Z) zwitterionic structures of the dye, in the femto- and picosecond timescales, depending on the strength of the intermolecular interactions with the solvent (see figure).

    5. Two-Component Membrane Lithography via Lipid Backfilling (pages 423–426)

      Seung-Yong Jung, Matthew A. Holden, Paul S. Cremer and C. Patrick Collier

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400540

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      A novel lithographic technique to pattern artificial lipid bilayer microdomains has been developed which exploits the limited mobility of gel-phase phospholipids. With this technique, fluid microdomains could be patterned into a solid gel-like matrix or gel-like lipids could be patterned in a sea of fluid lipids. In both cases, the patterned areas form a cohesive and contiguous supported lipid bilayer membrane (see picture).

    6. Isolated Nanoribbons of Carbon Nanotubes and Peapods (pages 426–430)

      Martin Kalbáč, Ladislav Kavan, Markéta Zukalová, Hana Pelouchová, Pavel Janda and Lothar Dunsch

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400374

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      Nanoribbons: A new method was developed for the preparation of aligned, isolated nanoribbons composed of carbon nanostructures (see figure). The method was applied to single- and double-walled carbon nanotubes, as well as to fullerene (C60) peapods. The deposited nanoribbons exhibit Raman features that are characteristic of the individual carbon nanostructures.

    7. A Barrier-Free Nonatomic Radical–Molecule Reaction: CCN+CH4 (pages 431–433)

      Jian Wang, Yi-hong Ding and Chia-chung Sun

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400456

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      Prototype for alkane reactions: The first barrierless reaction between a nonhydrogenated, nonatomic radical and methane, CCN+CH4 (see picture), is reported theoretically. The reaction proceeds via a carbene insertion mechanism, producing the predominant species C2H3CN plus H atom, whereas the recently proposed H-abstraction mechanism is endothermic and far less competitive. The title reaction is expected to play an important role in both combustion and interstellar processes

    8. IR Spectra of Isolated Arenium Ions: Hydroxyl and Halogen Substitution Effects on Aliphatic CH Bonds (pages 434–436)

      Nicola Solcà and Otto Dopfer

      Version of Record online: 11 FEB 2005 | DOI: 10.1002/cphc.200400531

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      Spectroscopy of protonated aromatic molecules: The properties of the reactive aliphatic CH2 group of simple substituted benzenium isomers (see figure) were studied in the gas phase by resonant IR photodissociation spectroscopy of weakly bound Ar or N2 clusters. The IR spectra directly probe the influence of H[RIGHTWARDS ARROW]OH/F/Cl substitution on the chemical properties of the reactive center in these important reaction intermediates free from interfering solvation effects.

    9. Infrared Spectroscopy of Protonated Phenylsilane in the Gas Phase (pages 437–440)

      Barbara Chiavarino, Maria E. Crestoni, Simonetta Fornarini, Joël Lemaire, Luke Mac Aleese and Philippe Maître

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400511

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      Gaseous ions: A variant of IR spectroscopy, developed to solve the structure of gaseous ions, was applied to the prototypical silyl-substituted arenium ion, [H3Si[BOND]C6H6]+. The experimental IR multiphoton-induced dissociation (IRMPD) spectrum is found to match the IR absorption features calculated for the ipso-protonated species (see figure).

    10. Direct Observation of Segregation of Sodium and Chloride Ions at an Ice Surface (pages 440–444)

      Jung-Hwan Kim, Taeho Shin, Kwang-Hwan Jung and Heon Kang

      Version of Record online: 11 FEB 2005 | DOI: 10.1002/cphc.200400429

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      Cold ice films provide a unique opportunity to take a snapshot of solvated ions in motion. The vertical distribution of Na+ and Cl ions at the surface of an ice film is measured using low-energy sputtering (LES; the picture shows LES intensities, I, for Na+ (▪) and Cl (○) ions) and reactive ion scattering techniques. The results directly reveal migration of Na+ ions from the surface to the interior of ice. This observation is in contrast to the surface residence of Cl ions.

    11. Equilibrium Coverage Fluctuations: A New Approach to Quantify Reversible Adsorption of Proteins (pages 444–448)

      Eike Lüthgens and Andreas Janshoff

      Version of Record online: 11 FEB 2005 | DOI: 10.1002/cphc.200400446

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      Binding kinetics of proteins on sensor devices: A new approach to simultaneously determine the rate constants of adsorption and desorption of proteins on surfaces at low coverage from the power spectrum of equilibrium coverage fluctuations is proposed and verified by dynamic Monte Carlo simulations (see picture).

    12. Covalent Linking of CdTe Nanocrystals to Amino-Functionalized Surfaces (pages 449–451)

      Alexey Shavel, Nikolai Gaponik and Alexander Eychmüller

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400516

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      CdTe-modified silicon wafers: Preliminarily aminated substrates of various compositions and shapes are linked with water-soluble, high-luminescent CdTe nanocrystals through the formation of an amide bond between the carboxylic groups of mercaptoacid-capped nanocrystals and the amino groups of the substrates (see picture).

    13. What are the Implications of Nonequilibrium in the O+OH and O+HO2 Reactions? (pages 453–465)

      A. J. C. Varandas

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400335

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      An exciting atmosphere: Local thermodynamic disequilibrium (LTD) can play a key role in describing the kinetics of the middle atmosphere. The excited products establish nonequilibrium in their concentrations, which affects the kinetics of the formation and destruction of HOx and Ox. There is no need for the downward adjustment of the ratio between the O+HO2 and O+OH reaction-rate constants that is suggested by simulations (see graphic; DMBE=double many-body expansion).

    14. Pressure Effects on Friedel–Crafts Alkylation Reactions in Supercritical Difluoromethane (pages 466–472)

      Andrew P. Abbott, Stuart Corr, Nicola E. Durling and Eric G. Hope

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400363

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      Reagent clustering is shown to affect the reaction dynamics and results in the ability to change the product distribution of a Friedel–Crafts (FC) alkylation reaction with pressure (see graphic). Dielectrometry is used as a novel technique for following the rate of an FC reaction in supercritical difluoromethane.

    15. Testing the Pairwise Additive Potential Approximation Using DFT: Coadsorption of CO and N on Rh(100) (pages 473–480)

      Daniel Curulla Ferré, Alexandre P. van Bavel and J. W. Niemantsverdriet

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400399

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      Coadsorption of CO and N: The pairwise additive potential approximation can be used to estimate the perturbation of the adsorption energy of an adsorbate (e.g., CO molecule) by coadsorbates (e.g., N atoms or other CO molecules). Density functional theory can simulate a temperature-programmed desorption spectrum (see graphic; n=number of CO molecules) and link the desorption features with actual microscopic configurations instead of adsorption sites.

    16. Fabrication of Ultrathin Films with Large Third-Order Nonlinear Optical Properties (pages 481–486)

      Li Jiang, Fushen Lu, Qing Chang, Yang Liu, Huibiao Liu, Yuliang Li, Wei Xu, Guanglei Cui, Junpeng Zhuang, Xiaofang Li, Shu Wang, Yinglin Song and Daoben Zhu

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400404

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      An ultrathin composite film containing anionic Ag-His complexes (His: L-Histidine) and oppositely charged poly(phenylenevinylene), BH-PPV, was fabricated by means of the electrostatic layer-by-layer self-assembly technique (see figure). UV/Vis spectra showed a continuous deposition process of the Ag-His complexes and BH-PPV. The structure and optical properties of the ultrathin film were investigated.

    17. Focal-Point Conformational Analysis of Ethanol, Propanol, and Isopropanol (pages 487–495)

      Kalju Kahn and Thomas C. Bruice

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400412

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      Correlation matters for molecular shape: The conformational energies of ethanol, propanol, and isopropanol strongly depend on electron correlation effects. Accurate results can be obtained by extrapolation to the basis-set limit. Calculations beyond the MP2 level may be necessary for conformational analysis (see figure).

    18. C[BOND]H⋅⋅⋅O Hydrogen Bonds in Cyclohexenone Reveal the Spectroscopic Behavior of Cmath image[BOND]H and Cmath image[BOND]H Donors (pages 496–502)

      Mariela M. Nolasco and Paulo J. A. Ribeiro-Claro

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400423

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      The carbonyl stretching mode, νC[DOUBLE BOND]O, and the C[BOND]H stretching modes, νC[BOND]H, can be used to probe the C[BOND]H⋅⋅⋅O hydrogen bonding in cyclohexenone (see picture). A surprising result is the absence of concentration- or temperature-dependent intensities in the bands assigned to the [DOUBLE BOND]C[BOND]H stretching modes.

    19. Theoretical Study of the Electronic Excited States of Tetracyanoethylene and Its Radical Anion (pages 503–510)

      Begoña Milián, Rosendo Pou-Amérigo, Manuela Merchán and Enrique Ortí

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400464

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      Evolution of the electronic spectrum upon reduction: By means of CASPT2 calculations, the absorption spectra of tetracyanoethylene (TCNE) and TCNE were rationalized (see graphic). The occurrence of a bound excited state for the anionic species is confirmed, and the data obtained with electron transmission spectroscopy are also analyzed.

    20. Through versus Cross Electron Delocalization in Polytriacetylene Oligomers: A Computational Analysis (pages 511–519)

      Maurizio Bruschi, Maria Grazia Giuffreda and Hans Peter Lüthi

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400202

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      Effective conjugation lengths: A systematic theoretical investigation is reported of the molecular and electronic properties of unsubstituted polytriacetylene (PTA) and iso-polytriacetylene oligomers (iso-PTA), which are characterized by through and cross π-conjugation pathways, respectively (see frontier orbitals). Differences in the effective conjugation length are directly related to electron delocalization in cross- and through-conjugated pathways.

    21. Crystallographic and Electrochemical Characteristics of La0.7Mg0.3Ni5.0−x(Al0.5Mo0.5)x Hydrogen-Storage Alloys (pages 520–525)

      Xin Bo Zhang, Dan Zi Sun, Wen Ya Yin, Yu Jun Chai and Min Shou Zhao

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400470

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      Positive results for negative electrodes: Alloys of the type La0.7Mg0.3Ni5.0−x(Al0.5Mo0.5)x (x=0–0.8) have been synthesised in view of their favourable hydrogen-storage properties. Structural analysis (see graphic) reveals the presence of La(La,Mg)2Ni9 and LaNi5 phases in all cases. The hydrogen-storage capacity can be optimised by controlling the Al and Mo content of the alloys.

    22. A Comparative Electrochemical Study of Diffusion in Room Temperature Ionic Liquid Solvents versus Acetonitrile (pages 526–533)

      Russell G. Evans, Oleksiy V. Klymenko, Paul D. Price, Stephen G. Davies, Christopher Hardacre and Richard G. Compton

      Version of Record online: 11 FEB 2005 | DOI: 10.1002/cphc.200400549

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      Diffusion processes in ionic liquids: The authors report a study on the translational diffusion of N,N,N′,N′-tetramethyl-para-phenylenediamine probe molecules (see picture) in acetonitrile and several ionic liquid solvents. Diffusion coefficients are found to follow the same relationship with temperature for both media types, but when the magnitude of the charge residing on the species in motion is varied, important differences become apparent.

    23. Simultaneous AFM Manipulation and Fluorescence Imaging of Single DNA Strands (pages 534–540)

      Andrew Hards, Chunqing Zhou, Markus Seitz, Christoph Bräuchle and Andreas Zumbusch

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400515

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      Tug of war with a single DNA molecule: Simultaneous atomic force manipulation and optical spectroscopy of a single molecule can be used to monitor the interplay between external force and optical spectra, as well as for the direct observation of nanomechanical processes. The authors demonstrate the first such experiments on fluorescently labeled single DNA molecules. Pulling on these can be observed directly until strand rupture occurs (see picture).

    24. High-Spin Chloro Mononuclear MnIII Complexes: A Multifrequency High-Field EPR Study (pages 541–546)

      Claire Mantel, Hongyu Chen, Robert H. Crabtree, Gary W. Brudvig, Jacques Pécaut, Marie-Noëlle Collomb and Carole Duboc

      Version of Record online: 18 FEB 2005 | DOI: 10.1002/cphc.200400484

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      High-field EPR is used to investigate the electronic properties of two synthetic six-coordinated mononuclear MnIII trichloro complexes. These systems complete a series of rhombic MnIII complexes, [Mn(L)(X)3] (X=F, N3). The comparison of their spin-Hamiltonian parameters shows that D is not sensitive to the nature of the anion, and that the high |E/D| value is in agreement with the distortions found in the octahedron (see graphic).

    25. Wetting of Surfactant Solutions by Alkanes (pages 547–555)

      Katherine M. Wilkinson, Colin D. Bain, Hiroki Matsubara and Makoto Aratono

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400514

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      First-order wetting transitions of alkanes on surfactant solutions are induced with increasing surfactant concentration due to variation of the interfacial tensions with surfactant adsorption. Below the transition concentration, the alkanes partially wet the surfactant solutions. Above the transition concentration, alkane molecules are solubilised into the surfactant monolayer to form a mixed monolayer in equilibrium with a bulk lens (see picture).

    26. Principles of Surface Physics. By Friedhelm Bechstedt. (pages 558–559)

      Gianfranco Pacchioni

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200400482

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      Preview: ChemPhysChem 3/2005 (page 562)

      Version of Record online: 4 MAR 2005 | DOI: 10.1002/cphc.200590002

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