ChemPhysChem

Cover image for ChemPhysChem

December 11, 2006

Volume 7, Issue 12

Pages 2441–2610

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Communications
    5. Articles
    6. Book Review
    7. Preview
    1. Cover Picture: Identification of the D3h Isomer of Carbon Trioxide (CO3) and Its Implications for Atmospheric Chemistry (ChemPhysChem 12/2006) (page 2441)

      Corey S. Jamieson, Alexander M. Mebel and Ralf I. Kaiser

      Article first published online: 4 DEC 2006 | DOI: 10.1002/cphc.200690038

      The cover picture shows the D3h isomer of carbon trioxide and the overlapping vibrational modes of different acyclic CO3 isotopomers. The D3h isomer of carbon trioxide is an important intermediate in atmospheric reactions between O and CO2. It has been experimentally detected for the first time by infrared spectroscopy after irradiating a carbon dioxide ice with energetic electrons. In their Article on page 2508 Jamieson et al. combine experiment with electronic structure calculation to identify the D3h isomer of carbon trioxide. The cloudy background photograph is a courtesy of Steve Hudson (www.hudsonphoto.com).

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Communications
    5. Articles
    6. Book Review
    7. Preview
  3. Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Communications
    5. Articles
    6. Book Review
    7. Preview
    1. Water Clusters in Crystal: Beyond the “Hydrogen-Bonding Graphs” (pages 2453–2455)

      Konstantin A. Lyssenko, Yulia V. Nelyubina, R. G. Kostyanovsky and Mikhail Yu. Antipin

      Article first published online: 9 NOV 2006 | DOI: 10.1002/cphc.200600549

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      Supramolecular assembly: The ordered tetrahydrate of piperidine-2-carboxylic acid (see figure) is analysed using X-ray diffraction with topological analysis of the electron density distribution function. This highly accurate method probes both the cooperativity effects of H-bonding and the influence of solute on water molecule aggregation in these polyhydrates.

    2. Computational Exploration of the Photocycloaddition of Imines to Alkenes (pages 2456–2459)

      Diego Sampedro

      Article first published online: 9 NOV 2006 | DOI: 10.1002/cphc.200600540

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      Structural requirements: The cycloaddition of imines to alkenes (see figure) is explored by photochemical calculations. The results provide an explanation for the experimental outcome and suggest some structural features that are required to make this reaction synthetically useful.

    3. Can a Blue Shift of the C[BOND]H Stretching Modes of Inactivated C Groups be an Indicator of Weak C[BOND]H⋅⋅⋅O Hydrogen Bonds? (pages 2460–2463)

      Zheng Xu, Haoran Li and Congmin Wang

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600486

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      Anyone for TEA? By means of a combined spectroscopic and theoretical study of TEA–[D6]acetone, TEA–CCl4, and TEA–CDCl3 mixtures, the hydrogen bonds formed at the nitrogen site are found to play an important role in the blue shift of the stretching modes of the methylene bond, υC−H (see figure).

    4. Dipole Moment, Hydrogen Bonding and IR Spectrum of Confined Water (pages 2464–2467)

      François-Xavier Coudert, Rodolphe Vuilleumier and Anne Boutin

      Article first published online: 17 NOV 2006 | DOI: 10.1002/cphc.200600561

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      Theoretically speaking: Water confined in a hydrophobic zeolite with large interconnected pores (see figure) is investigated using the Car–Parrinello molecular dynamics method (CPMD). The thermodynamic and electronic properties and the vibrational infrared spectrum of the confined water are determined. The infrared spectrum of the structural zeolite indicates that only a very small interaction between the host and the guest species occurs.

    5. Optical and Electrochemical Properties of CeO2 Spindles (pages 2468–2470)

      Dong-En Zhang, Xiao-Jun Zhang, Xiao-Min Ni, Ji-Mei Song and Hua-Gui Zheng

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600388

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      Nanostructured ceria: The optical and electrochemical properties of thermally synthesized CeO2 spindles are investigated (see figure). The obtained CeO2 nanoparticles show interesting properties for applications as new electrode materials.

    6. Control of Molecular Fragmentation Using Binary Phase-Shaped Femtosecond Laser Pulses (pages 2471–2473)

      Vadim V. Lozovoy, Tissa C. Gunaratne, Janelle C. Shane and Marcos Dantus

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600283

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      Laser control of chemical reactions: Orders of magnitude control over the relative yield of products is achieved using binary shaped femtosecond laser pulses. Transform-limited pulses (- - - - -) produce ions with an intact aromatic ring; highly modulated pulses (—) yield smaller mass fragments. The pathway involving isomerization of the nitro group is insensitive to phase modulation.

    7. trans-Stilbene Incorporation in Acidic Medium-Pore ZSM-5 Zeolite: A Pulsed EPR Study (pages 2474–2477)

      Hervé Vezin, Alain Moissette, Matthieu Hureau and Claude Brémard

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600279

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      Entrapped radicals: trans-Stilbene (C6H5[BOND]CH[DOUBLE BOND]CH[BOND]C6H5, t-St) entrapment in medium-pore acidic HnZSM-5 zeolites induces t-St ionization and subsequent electron transfer. The aluminium-rich ZSM-5 participates both as electron acceptor and donor to the unusual stabilization of the t-St@HnZSM-5.+.− electron–hole pair. Pulsed electron paramagnetic resonance (EPR; see picture) spectroscopy provides a realistic picture of the chemical environments of the unpaired electrons.

    8. Design of the Sandwich-like Compounds Based on the All-Metal Aromatic Unit Al3 (pages 2478–2482)

      Li-ming Yang, Yi-hong Ding and Chia-chung Sun

      Article first published online: 4 DEC 2006 | DOI: 10.1002/cphc.200600564

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      Hetero-assembly: Sandwich-like complexes containing Al3 assemble in a “hetero-decked sandwich” scheme where cluster fusion is avoided. The all-metal aromaticity of Al3 is preserved in the complex CpMAl3q− (see figure) and this theoretical study supports the experimental identification of the Al62− anion (with M+ counterions).

    9. Solvent Effect on Optical Rotation: A Case Study of Methyloxirane in Water (pages 2483–2486)

      Parag Mukhopadhyay, Gérard Zuber, Michael-Rock Goldsmith, Peter Wipf and David N. Beratan

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600477

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      Explicit solute–solvent interactions: MD simulations and TD-DFT are used to determine the solvent dependence of the optical rotatory dispersion (ORD) for methyloxirane in water (see figure). The inclusion of explicit solute–solvent interactions is essential to describe the influence of the solvent on the OR of the system and the MD simulations provide a suitable means to analyze and predict chiroptical solvation effects.

    10. Interplay Between Cation–π, Anion–π and π–π Interactions (pages 2487–2491)

      David Quiñonero, Antonio Frontera, Carolina Garau, Pablo Ballester, Antoni Costa and Pere M. Deyà

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600343

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      Strong synergic effects: A computational MP2 study proves that very strong synergic effects are present in complexes where cation–π, anion–π and π–π interactions coexist (see figure). The interactions have been analyzed using Bader′s theory of “atoms in molecules” and the energetic-partition scheme of the molecular interaction potential with polarization.

    11. Pure White-Light Emission of Nanocrystal–Polymer Composites (pages 2492–2496)

      Haizhu Sun, Junhu Zhang, Hao Zhang, Yu Xuan, Chunlei Wang, Minjie Li, Ye Tian, Yang Ning, Dongge Ma, Bai Yang and Zhi Yuan Wang

      Article first published online: 10 NOV 2006 | DOI: 10.1002/cphc.200600480

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      White-light emitter: A convenient and general method for the preparation of composites with pure and stable white-light photoluminescence and electroluminescence from fluorescent nanocrystals (NCs) and functional polymers is developed (see figure; FRET=Förster resonance energy transfer)). Through electrostatic interaction the distance of the charged polymers and the NCs is shortened so that efficient electron transfer occurs at the interface.

  4. Articles

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Communications
    5. Articles
    6. Book Review
    7. Preview
    1. Behavior of Temperature-Sensitive PNIPAM Confined in Polyelectrolyte Capsules (pages 2497–2502)

      Michelle Prevot, Christophe Déjugnat, Helmuth Möhwald and Gleb B. Sukhorukov

      Article first published online: 7 NOV 2006 | DOI: 10.1002/cphc.200600167

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      Temperature-sensitive collapse: The lower critical solution temperature of poly(N-isopropylacrylamide) encapsulated inside polyelectrolyte microcapsules is studied in dependence of the nature and the amount of different salts added to the system. The ability to tune and finely control the temperature-sensitive collapse of encapsulated PNIPAM (see series of confocal pictures) is demonstrated and shows potential for use in microsensors or drug-delivery systems.

    2. Carbon Nanorings: A Challenge to Theoretical Chemistry (pages 2503–2507)

      I. García Cuesta, T. B. Pedersen, H. Koch and A. Sánchez de Merás

      Article first published online: 23 OCT 2006 | DOI: 10.1002/cphc.200600362

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      Importance of dispersion forces: High-level ab initio calculations show that the interactions in the complex HMB@6-CPPA (see figure) can only be rationalized if dispersion forces are taken into account. Therefore, the commonly used density functional theory (DFT) methods are not well suited to describe this kind of molecular species.

    3. Identification of the D3h Isomer of Carbon Trioxide (CO3) and Its Implications for Atmospheric Chemistry (pages 2508–2513)

      Corey S. Jamieson, Alexander M. Mebel and Ralf I. Kaiser

      Article first published online: 9 OCT 2006 | DOI: 10.1002/cphc.200600390

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      Geometry is the key: Low-temperature spectroscopy experiments combined with electronic structure calculations identify for the first time the elusive D3h isomer of CO3 (see figure). A new one-step formation route of this important reaction intermediate is proposed to explain the isotope enrichment of 18O in stratospheric carbon dioxide.

    4. Two-Photon Photochromism of a Diarylethene Enhanced by Förster Resonance Energy Transfer from Two-Photon Absorbing Fluorenes (pages 2514–2519)

      Kevin D. Belfield, Mykhailo V. Bondar, Claudia C. Corredor , Florencio E. Hernandez, Olga V. Przhonska and Sheng Yao

      Article first published online: 13 NOV 2006 | DOI: 10.1002/cphc.200600553

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      Two-photon photochromism: Two-photon excitation can be used to initiate photochromic transformations of a diarylethene (such as diarylethene 1). The resonance energy transfer (RET) from the emission of two-photon absorbing fluorene derivatives (such as fluorene 3) is explored as a tool to increase the nonlinear performance of diarylethenes. Förster-type RET in solution is observed.

    5. Enhancement of Photocurrent Generation by Honeycomb Structures in Organic Thin Films (pages 2520–2525)

      Liping Heng, Jin Zhai, Yong Zhao, Jinjie Xu, Xianliang Sheng and Lei Jiang

      Article first published online: 14 NOV 2006 | DOI: 10.1002/cphc.200600393

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      Top performance: Ordered honeycomb structures, introduced into thin films of a light-emitting block copolymer, significantly improve its photoelectric conversion behavior (see figure). Increased photocurrents generated in the honeycomb (porous) films compared to the smooth films clearly indicate their superiority.

    6. A Theoretical Investigation of the Gas-Phase Oxidation Reaction of the Saturated tert-Butyl Radical (pages 2526–2532)

      Jong-Ho Choi, Mi-Ja Nam and Sung-Eui Youn

      Article first published online: 8 NOV 2006 | DOI: 10.1002/cphc.200600473

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      Radical insights: A theoretical study explores the radical–radical reaction mechanisms and dynamics of ground-state atomic oxygen [O(3P)] with the saturated tert-butyl radical. The lowest doublet potential energy surface is examined and two distinctive reaction pathways, abstraction and addition are presented.

    7. Temperature Dependence of Ultra-Exothermic Charge Recombinations (pages 2533–2539)

      Carlos Serpa, Paulo J. S. Gomes, Luis G. Arnaut, J. Seixas de Melo and Sebastião J. Formosinho

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600467

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      Nuclear tunneling: A very weak temperature dependence is found for the rates of ultra-exothermic charge recombinations (see figure). The obtained results confirm the absence of solvent effects and the relevance of nuclear tunneling in charge recombinations.

    8. Photoelectrochemical Behavior of Nanostructured WO3 Thin-Film Electrodes: The Oxidation of Formic Acid (pages 2540–2551)

      Damián Monllor-Satoca, Luis Borja, Antonio Rodes, Roberto Gómez and Pedro Salvador

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600379

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      The hole story: The photooxidation of formic acid is studied on WO3 thin-film electrodes prepared by both electrode position and deposition from a nanopowder slurry. From the proposed kinetic model, a direct hole-transfer mechanism through an adsorbed state is envisaged. The molecular adsorption of formic acid is confirmed by attenuated total reflection infrared spectroscopy (see picture).

    9. Organic Molecular Beam Deposition of Oligophenyls on Au(111): A Study by X-ray Absorption Spectroscopy (pages 2552–2558)

      Stefan Müllegger, Kathrin Hänel, Thomas Strunskus, Christof Wöll and Adolf Winkler

      Article first published online: 9 NOV 2006 | DOI: 10.1002/cphc.200600353

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      Inter-ring twisting: As revealed by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, p-quaterphenyl and p-hexaphenyl adsorbed on a Au(111) surface show an inter-ring twisting of 30–40°, similar to the gas-phase conformation. The molecules lie flat on the surface up until half-monolayer coverage then, in the saturated monolayer, the second half of the molecules are side-tilted (see picture).

    10. Compartmental Modeling of the Fluorescence Anisotropy Decay of a Cylindrically Symmetric Brownian Rotor: Identifiability Analysis (pages 2559–2566)

      Noël Boens, Eugene Novikov and Marcel Ameloot

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600309

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      Molecular rotation is studied by time-resolved fluorescence anisotropy, for which an alternative matrix description in the case of a cylindrically symmetric Brownian rotor is given. The identifiability analysis of this model (see picture) shows that the rotational diffusion constants can be uniquely determined, whereas the orientations of the transition moments of excitation and emission are not uniquely identifiable.

    11. Magnetic Properties of Poly(propylene imine)–Copper Dendromesogenic Complexes: An EPR Study (pages 2567–2577)

      Natalia Domracheva, Anisoara Mirea, Markus Schwoerer, Laura Torre-Lorente and Günter Lattermann

      Article first published online: 7 NOV 2006 | DOI: 10.1002/cphc.200600360

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      Complex bridges: A redox-active CuII dendromesogenic complex and the CuII nitrate electron transfer associated with valence tautomerism are revealed in copper-based dendrimers. The complex is a mixed-valence dimer containing Cu ions and an antiferromagnetically coupled NO3. radical (see picture). The activation energy for the electron transfer of 0.35 meV indicates low-energy charge dynamics.

    12. First Principles and Experimental 1H NMR Signatures of Solvated Ions: The Case of HCl(aq) (pages 2578–2584)

      Tatiana Murakhtina, Jasper Heuft, Evert Jan Meijer and Daniel Sebastiani

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600385

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      Shift work: The 1H NMR chemical shift distribution of an aqueous HCl solution is calculated as a function of concentration, based on molecular dynamics simulations. The chemical shifts are compared with experimental spectra obtained by liquid-state 1H NMR experiments. The ab initio proton shifts are decomposed into contributions from Eigen/Zundel cations, the first solvation shells of the Cl ions, and regular water molecules (see picture).

    13. A New Method for the Study of Processes at the Liquid–Liquid Interface Using an Array of Microdroplets on a Au Electrode (pages 2585–2592)

      Andrew O. Simm, François G. Chevallier, Olga Ordeig, F. Javier del Campo, Francesc X. Munoz and Richard G. Compton

      Article first published online: 7 NOV 2006 | DOI: 10.1002/cphc.200600394

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      Blocking diffusion: The fabrication of a regular array of microdroplets on a gold electrode surface is studied. By voltametrically monitoring the transport-controlled reduction rate of CuII at the unblocked part of the electrode (see figure) it is possible to deduce, via simulation, the parameters controlling the rate of uptake of CuII at the droplet–aqueous solution interface as the droplet “fills up” with CuII.

    14. Theoretical Investigations on the Geometric and Electronic Structures of Phenylene-Acetylene Macrocycles (pages 2593–2600)

      Yanwei Li, Jianwei Zhao, Xing Yin and Geping Yin

      Article first published online: 30 OCT 2006 | DOI: 10.1002/cphc.200600416

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      PAM conformations: Phenylene-acetylene macrocycles (PAM) are investigated theoretically. The big macrocycles, such as 7PAM, 8PAM, and 9PAM, usually favor nonplanar conformations in which the ring-strain energy is reduced. The figure shows the HOMO and LUMO spatial distributions of PAMs in planar conformation.

    15. Ice Recrystallization Inhibition and Molecular Recognition of Ice Faces by Poly(vinyl alcohol) (pages 2601–2606)

      Carsten Budke and Thomas Koop

      Article first published online: 16 NOV 2006 | DOI: 10.1002/cphc.200600533

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      Breaking the ice: Ostwald ripening of polycrystalline ice can be inhibited by small amounts of poly(vinyl alcohol) (PVA; left picture). The habit of ice single crystals growing in aqueous solutions containing PVA reveals that PVA adsorbs to the primary and secondary prism faces of ice (right picture). A molecular mechanism for adsorption of PVA to ice is proposed.

  5. Book Review

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Communications
    5. Articles
    6. Book Review
    7. Preview
  6. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Communications
    5. Articles
    6. Book Review
    7. Preview
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      Preview: ChemPhysChem 12/2006 (page 2610)

      Article first published online: 4 DEC 2006 | DOI: 10.1002/cphc.200690040

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