ChemPhysChem

Cover image for Vol. 14 Issue 6

April 15, 2013

Volume 14, Issue 6

Pages 1085–1292

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Highlight
    7. Concept
    8. Communications
    9. Articles
    1. You have free access to this content
      Cover Picture: On the Photoabsorption by Permanganate Ions in Vacuo and the Role of a Single Water Molecule. New Experimental Benchmarks for Electronic Structure Theory (ChemPhysChem 6/2013) (page 1085)

      Jørgen Houmøller, Sydney H. Kaufman, Dr. Kristian Støchkel, Prof. Lokesh C. Tribedi, Prof. Steen Brøndsted Nielsen and Prof. J. Mathias Weber

      Article first published online: 8 APR 2013 | DOI: 10.1002/cphc.201390026

      Thumbnail image of graphical abstract

      In solutions the interaction of ions with solvent often changes the solute properties, which is reflected in the absorption spectrum of the solute (solvatochromism). For some ions a single water molecule has a large effect, while others only display significant changes upon full hydration. Predicting electronic spectra in the presence of solvent is still a challenge for electronic structure theory, so experimental data on prototype solute ions with and without the presence of solvent are important benchmarks. S. Brøndsted Nielsen, J. M. Weber et al. show how solvation affects the electronic spectrum of permanganate on p. 1133.

    2. You have free access to this content
      Inside Cover: Understanding Photophysical Effects of Cucurbituril Encapsulation: A Model Study with Acridine Orange in the Gas Phase (ChemPhysChem 6/2013) (page 1086)

      Martin F. Czar and Prof. Rebecca A. Jockusch

      Article first published online: 8 APR 2013 | DOI: 10.1002/cphc.201390027

      Thumbnail image of graphical abstract

      Gas-phase spectral and time-resolved fluorescence measurements of a model cationic dye and its host–guest complex with cucurbit[7]uril provide insight into the complexity of dye-tuning with macrocycles, as shown on p. 1138 ff. by M. F. Czar and R. A. Jockusch.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Highlight
    7. Concept
    8. Communications
    9. Articles
    1. Graphical Abstract: ChemPhysChem 6/2013 (pages 1087–1095)

      Article first published online: 8 APR 2013 | DOI: 10.1002/cphc.201390028

  3. Editors' Selection

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Highlight
    7. Concept
    8. Communications
    9. Articles
    1. Editors' Selection: ChemPhysChem 6/2013 (page 1096)

      Article first published online: 8 APR 2013 | DOI: 10.1002/cphc.201390029

  4. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Highlight
    7. Concept
    8. Communications
    9. Articles
  5. Highlight

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Highlight
    7. Concept
    8. Communications
    9. Articles
    1. Cucurbituril Hosts in Real-Life Action (pages 1107–1108)

      Prof. Angel E. Kaifer

      Article first published online: 4 MAR 2013 | DOI: 10.1002/cphc.201300147

      Thumbnail image of graphical abstract

      Stick it to them! Underwater adhesion becomes possible by taking advantage of highly stable host–guest complexes formed between cucurbit[7]uril hosts and ferrocenyl residues. The formation of multiple noncovalent complexes between the two complementary surfaces gives rise to strong adhesive forces resulting in a “supramolecular velcro” system that operates efficiently in the presence of water.

  6. Concept

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Highlight
    7. Concept
    8. Communications
    9. Articles
    1. Hydrodynamic Model for Plasmonics: A Macroscopic Approach to a Microscopic Problem (pages 1109–1116)

      Dr. Cristian Ciracì, Prof. Sir John B. Pendry and Prof. Dr. David R. Smith

      Article first published online: 19 MAR 2013 | DOI: 10.1002/cphc.201200992

      Thumbnail image of graphical abstract

      Response of the electrons: The hydrodynamic model captures much of the microscopic dynamics relating to the fundamental nature of electrons. The figure shows a plot of the induced charge-density distribution for two coupled circular metal wires.

  7. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Highlight
    7. Concept
    8. Communications
    9. Articles
    1. Cooperative Behaviour of Pt Microelectrodes during CO Bulk Electrooxidation (pages 1117–1121)

      D. Alfonso Crespo-Yapur, Dr. Antoine Bonnefont, Prof. Dr. Rolf Schuster, Prof. Dr. Katharina Krischer and Prof. Dr. Elena R. Savinova

      Article first published online: 1 MAR 2013 | DOI: 10.1002/cphc.201300105

      Thumbnail image of graphical abstract

      Cooperative behaviour of an array of microelectrodes: The interplay of bistable reaction kinetics with global coupling results in a spontaneous sequential activation of electrodes when the applied current is increased.

    2. What Are the Active Species in the Photoinduced H2 Production with Terpyridyl Pt(II) Complexes? An Investigation by in Situ XAFS (pages 1122–1125)

      Dr. Martin Martis, Prof. Dr. Kohsuke Mori, Dr. Kazuo Kato, Prof. Dr. Gopinathan Sankar and Prof. Dr. Hiromi Yamashita

      Article first published online: 6 MAR 2013 | DOI: 10.1002/cphc.201201093

      Thumbnail image of graphical abstract

      Origin of the species: In situ X-ray absorption measurements show that monomeric Pt(II) species are the active components for photocatalytic H2 evolution under visible-light illumination for both [PtCl(tpy)]Cl on its own and a three-component system comprising Ru(bpy)3Cl2, MV2+ and [PtCl(tpy)]Cl in the presence of a sacrificial electron donor (EDTA).

    3. Bioactive Formulations with Sugar-Derived Surfactants: A New Approach for Photoprotection and Controlled Release of Promethazine (pages 1126–1131)

      Dr. Cécile Bize, Dr. Jean-Christophe Garrigues, Dr. Jean-Pierre Corbet, Dr. Isabelle Rico-Lattes and Dr. Muriel Blanzat

      Article first published online: 22 FEB 2013 | DOI: 10.1002/cphc.201200932

      Thumbnail image of graphical abstract

      Skin deep: A bioactive formulation for dermal delivery of antihistamines is obtained by using the original properties of catanionic associations towards self-assembly in water. The drug, which participates in its own transport, is preserved from photodegradation when solubilised in the bioactive formulation. The drug release through the skin is also delayed.

  8. Articles

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Highlight
    7. Concept
    8. Communications
    9. Articles
    1. On the Photoabsorption by Permanganate Ions in Vacuo and the Role of a Single Water Molecule. New Experimental Benchmarks for Electronic Structure Theory (pages 1133–1137)

      Jørgen Houmøller, Sydney H. Kaufman, Dr. Kristian Støchkel, Prof. Lokesh C. Tribedi, Prof. Steen Brøndsted Nielsen and Prof. J. Mathias Weber

      Article first published online: 1 FEB 2013 | DOI: 10.1002/cphc.201300019

      Thumbnail image of graphical abstract

      New light on permanganate: Electronic spectra of MnO4 and its complex with a single water molecule are measured in vacuo by photodissociation action spectroscopy of the mass-selected parent ions. The spectra are red-shifted by 0.15 eV compared to the spectrum obtained for the ions in aqueous solution. The data provide the best experimental benchmarks for electronic structure calculations on these prototypical metal tetroxo ions.

    2. Understanding Photophysical Effects of Cucurbituril Encapsulation: A Model Study with Acridine Orange in the Gas Phase (pages 1138–1148)

      Martin F. Czar and Prof. Rebecca A. Jockusch

      Article first published online: 25 FEB 2013 | DOI: 10.1002/cphc.201201008

      Thumbnail image of graphical abstract

      CB, or not CB: How the confined, hydrophobic environment offered by the interior of cucurbiturils (CBs) in some ways resembles the gas phase, and in other ways does not.

    3. An Interplay of Cooperativity between Cation⋅⋅⋅π, Anion⋅⋅⋅π and C[BOND]H⋅⋅⋅Anion Interactions (pages 1149–1154)

      Prof. Dr. Tarun K. Mandal, Siddhartha Samanta, Sourav Chakraborty and Prof. Dr. Ayan Datta

      Article first published online: 19 MAR 2013 | DOI: 10.1002/cphc.201300128

      Thumbnail image of graphical abstract

      United we stand! Cooperative interactions between the attractive cation⋅⋅⋅π and C[BOND]H⋅⋅⋅anion interactions and the repulsive anion⋅⋅⋅π interactions stabilize supramolecular systems.

    4. Molecular Suction Pads: Self-Assembled Monolayers of Subphthalocyaninatoboron Complexes on Gold (pages 1155–1160)

      Dr. Ulrich Glebe, Dr. Joe E. Baio, Prof. Líney Árnadóttir, Prof. Ulrich Siemeling and Dr. Tobias Weidner

      Article first published online: 25 MAR 2013 | DOI: 10.1002/cphc.201300074

      Thumbnail image of graphical abstract

      Lying low: A detailed analysis of thin films of subphthalocyaninatoboron derivatives self-assembled from solution onto gold surfaces is presented. The molecules are present on the substrate in a predominantly flat adsorption geometry, resembling a suction pad on a surface.

    5. Enhanced Li Adsorption and Diffusion in Single-Walled Silicon Nanotubes: An ab Initio Study (pages 1161–1167)

      Vadym V. Kulish, Dr. Man-Fai Ng, Oleksandr I. Malyi, Prof. Ping Wu and Prof. Zhong Chen

      Article first published online: 8 APR 2013 | DOI: 10.1002/cphc.201300004

      Thumbnail image of graphical abstract

      Enhancing Li diffusion: Li adsorption and diffusion in single-walled Si nanotubes (SWSiNTs) of interest to Li-ion battery anodes are studied theoretically. SWSiNTs show a higher reactivity toward the adsorption of Li atoms compared to carbon nanotubes (CNTs) and Si nanoclusters. A lower energy barrier for penetration of the Li atoms into the nanotubes through the sidewalls is found relative to that for CNTs, which may suggest enhanced Li diffusion rates.

    6. Electron Transfer between Hydrogen-Bonded Pyridylphenols and a Photoexcited Rhenium(I) Complex (pages 1168–1176)

      Dr. William Herzog, Dr. Catherine Bronner, Susanne Löffler, Dr. Bice He, Daniel Kratzert, Prof. Dietmar Stalke, Prof. Andreas Hauser and Prof. Oliver S. Wenger

      Article first published online: 22 FEB 2013 | DOI: 10.1002/cphc.201201069

      Thumbnail image of graphical abstract

      A concerted effort: Two pyridylphenols with intramolecular hydrogen bonds react with a metal complex through concerted proton transfer (PT)–electron transfer (ET). Upon photoexcitation of the complex, ET occurs from the phenol to the metal, and the phenolic proton is transferred to the pyridine moiety (see picture; MLCT=metal-to-ligand charge transfer).

    7. Supramolecular Cl⋅⋅⋅H and O⋅⋅⋅H Interactions in Self-Assembled 1,5-Dichloroanthraquinone Layers on Au(111) (pages 1177–1181)

      Seung-Kyun Noh, Jeong Heum Jeon, Won Jun Jang, Dr. Howon Kim, Soon-Hyeong Lee, Min Wook Lee, Prof. Jhinhwan Lee, Prof. Seungwu Han and Prof. Se-Jong Kahng

      Article first published online: 4 MAR 2013 | DOI: 10.1002/cphc.201201061

      Thumbnail image of graphical abstract

      Halogen interaction: Supramolecular interactions in the two-dimensional self-assembled layers of 1,5-dichloroanthraquinones on Au(111) are studied using scanning tunneling microscopy and density functional calculations. Intermolecular Cl⋅⋅⋅H and O⋅⋅⋅H hydrogen bonds stabilize two different molecular structures. Cl-related halogen bonds marginally contribute to this stabilization due to the modest positive potential (σ hole) of the Cl ligands.

    8. Energies and Spin States of FeS0/−, FeS20/−, Fe2S20/−, Fe3S40/−, and Fe4S40/− Clusters (pages 1182–1189)

      Yan-Ni Li, Dr. Shengguang Wang, Tao Wang, Rui Gao, Dr. Chun-Yu Geng, Dr. Yong-Wang Li, Dr. Jianguo Wang and Dr. Haijun Jiao

      Article first published online: 7 MAR 2013 | DOI: 10.1002/cphc.201201043

      Thumbnail image of graphical abstract

      Calculated attraction: The structures and energies of the electronic ground states of the FeS0/−, FeS20/−, Fe2S20/−, Fe3S40/−, and Fe4S40/− neutral and anionic clusters are computed systematically with nine computational methods in combination with seven basis sets (see picture; AEA=adiabatic electronic affinities).

    9. Modeling Diffusion in Foamed Polymer Nanocomposites (pages 1190–1196)

      Sandeep Ippalapalli, A. Dileep Ranaprathapan, Dr. Sachchida N. Singh and Dr. G. Harikrishnan

      Article first published online: 5 MAR 2013 | DOI: 10.1002/cphc.201200977

      Thumbnail image of graphical abstract

      In and out: Two-way multicomponent diffusion in polymer nanocomposite foams is investigated by simulations and thermal conductivity measurements. Variations in the aspect ratio of the filler, filler-polymer interfacial interactions, and the volume fraction of the filler are considered. Simulations of the thermal conductivity are in good agreement with experiments for low and medium aspect-ratio fillers but show deviations at higher aspect ratios.

    10. Fluorescence Quenching over Short Range in a Donor-DNA-Acceptor System (pages 1197–1204)

      Dr. Thomas Ehrenschwender, Dr. Yu Liang, Dr. Andreas-Neil Unterreiner, Prof. Dr. Hans-Achim Wagenknecht and Dr. Thomas J. A. Wolf

      Article first published online: 26 MAR 2013 | DOI: 10.1002/cphc.201200924

      Thumbnail image of graphical abstract

      Hop along: A new donor-DNA-acceptor system is synthesized containing Nile red-modified 2′-deoxyuridine as charge donor and 6-N,N-dimethylaminopyrene-modified 2′-deoxyuridine as acceptor to investigate the charge transfer in DNA duplexes (see picture) using fluorescence spectroscopy and time-resolved femtosecond pump-probe techniques.

    11. Synthesis of CuCorePtShell Nanoparticles as Model Structures for Core–Shell Electrocatalysts by Direct Platinum Electrodeposition on Copper (pages 1205–1210)

      Dr. Christian Kulp, Konrad Gillmeister, Prof. Dr. Wolf Widdra and Prof. Michael Bron

      Article first published online: 5 MAR 2013 | DOI: 10.1002/cphc.201200891

      Thumbnail image of graphical abstract

      Cu nanoparticles are prepared on glassy-carbon electrodes by electrodeposition; the subsequent deposition of Pt leads to core–shell particles. XPS and electrochemical techniques are combined to unveil the core–shell structure of the obtained materials.

    12. Domain-Averaged Exchange-Correlation Energies as a Physical Underpinning for Chemical Graphs (pages 1211–1218)

      Prof. M. García-Revilla, Prof. E. Francisco, Paul L. A. Popelier and Prof. Angel Martín Pendás

      Article first published online: 28 MAR 2013 | DOI: 10.1002/cphc.201300092

      Thumbnail image of graphical abstract

      Draw me a molecule: The spatial distribution of atoms in a molecule in the form of chemical graphs is obtained for a set of molecules, using their corresponding domain-averaged exchange-correlation energies (Vxc). Conveniently, such energies are transferable (for 1, n interactions in saturated linear hydrocarbons) and can provide an accurate estimation of the covalent-like contribution between pairs of given interacting topological atoms A and B.

    13. Molecular Switching Behavior in Isosteric DNA Base Pairs (pages 1219–1226)

      A. K. Jissy, Sukanya Konar and Prof. Dr. Ayan Datta

      Article first published online: 20 FEB 2013 | DOI: 10.1002/cphc.201201083

      Thumbnail image of graphical abstract

      Paired up: The structures and proton-coupled behavior of adenine–thymine and a modified base pair containing a thymine isostere, adenine–difluorotoluene (A-F), are studied in different solvents by dispersion-corrected density functional theory. DNA sequences capable of changing their sequence conformation on protonation are used in the construction of pH-based molecular switches (see picture).

    14. Vibrational Sum-Frequency Generation Activity of a 2,4-Dinitrophenyl Phospholipid Hybrid Bilayer: Retrieving Orientational Parameters from a DFT Analysis of Experimental Data (pages 1227–1236)

      Dr. Dan Lis, Dr. Julien Guthmuller, Prof. Dr. Benoît Champagne, Dr. Christophe Humbert, Dr. Bertrand Busson, Dr. André Peremans and Dr. Francesca Cecchet

      Article first published online: 3 APR 2013 | DOI: 10.1002/cphc.201201063

      Thumbnail image of graphical abstract

      Nonlinear vibrational response of a hybrid bilayer of 2,4-dinitrophenyl phospholipid (DNP) supported on a Pt surface is interpreted qualitatively and quantitatively by sum-frequency generation spectroscopy and density functional theory calculations. Spectral simulations also reveal the orientation of the 2,4-dinitrophenyl polar head of DNP, which is estimated to have tilt and rotation angles of 45±5° and 0±30°, respectively (see picture).

    15. Physicochemical Characterization of Acidiphilium sp. Biofilms (pages 1237–1244)

      Dr. Moustafa Malki, Dr. Santiago Casado, Dr. María Francisca López, Dr. Renaud Caillard, Dr. F. Javier Palomares, Dr. José A. Martín Gago, Dr. Cristina Vaz-Domínguez, Dr. Angel Cuesta, Prof. Ricardo Amils, Prof. Víctor M. Fernández, Dr. Marisela Velez, Dr. Antonio L. De Lacey and Dr. David Olea

      Article first published online: 1 MAR 2013 | DOI: 10.1002/cphc.201201034

      Thumbnail image of graphical abstract

      Acidiphilium biofilms are grown on graphitic flakes and are characterized by different physicochemical techniques. Combined fluorescence–AFM microscopy is applied to study the biofilm formation over time and to detect nanosized particles that are, in turn, analyzed by X-ray photoelectron spectroscopy and attenuated total reflection surface-enhanced infrared absorption spectroscopy.

    16. Phase Stability and Elastic Properties of Chromium Borides with Various Stoichiometries (pages 1245–1255)

      Dr. Bing Wang, Dr. De Yu Wang, Dr. Zhenxiang Cheng, Prof. Dr. Xiaolin Wang and Prof. Dr. Yuan Xu Wang

      Article first published online: 25 FEB 2013 | DOI: 10.1002/cphc.201201009

      Thumbnail image of graphical abstract

      Mix and match: Two new structures of CrB3 (P-6m2 and Pmmn) are predicted by using a newly developed particle swarm optimization (PSO) algorithm and the experimental structures of CrB4 (Immm and Pnnm) are also reproduced successfully (see picture). The strong covalent Cr[BOND]B bonding in CrB4 induced hardness and the Pnnm phase is thermodynamically stable up to 100 GPa.

    17. Theoretical Investigation of the Coupling between Hydrogen-Atom Transfer and Stacking Interaction in Adenine–Thymine Dimers (pages 1256–1263)

      Dr. Giovanni Villani

      Article first published online: 12 MAR 2013 | DOI: 10.1002/cphc.201200971

      Thumbnail image of graphical abstract

      Back to base: Three different dimers of the adenine–thymine base pair are studied to reveal the changes of structure, atomic charge, and energy induced by coupling between the movement of atoms in the hydrogen bonds and the stacking interaction (see picture). The coupling depends on the dimer considered and is different for the N[BOND]N and N[BOND]O hydrogen bonds.

    18. Theoretical Study on the Photodegradation Mechanism of Nona-BDEs in Methanol (pages 1264–1271)

      Lu Pan and Prof. Wensheng Bian

      Article first published online: 20 FEB 2013 | DOI: 10.1002/cphc.201200952

      Thumbnail image of graphical abstract

      Break up the family: A photochemical study on the degradation of a set of polybrominated diphenyl ethers (PBDE) congeners is presented, using a model of combined time-dependent DFT and polarizable continuum. Photodegradation triggered by sunlight exposure is found to be due to the electronic transitions from π to σ* orbitals located on the tetra-brominated phenyl, followed by an electron transfer towards the particular C[BOND]Br bond.

    19. Bare Clusters Derived from Protein Templates: Au25+, Au38+ and Au102+ (pages 1272–1282)

      Ananya Baksi, Prof. Dr. Thalappil Pradeep, Dr. Bokwon Yoon, Dr. Constantine Yannouleas and Prof. Dr. Uzi Landman

      Article first published online: 18 MAR 2013 | DOI: 10.1002/cphc.201200927

      Thumbnail image of graphical abstract

      Bare gold cluster ions of specific nuclearity are formed in the gas phase upon laser irradiation of protein–Au+ adducts.

    20. Scanning Probe Microscopy beyond Imaging: A General Tool for Quantitative Analysis (pages 1283–1292)

      Dr. Andrea Liscio

      Article first published online: 22 FEB 2013 | DOI: 10.1002/cphc.201200880

      Thumbnail image of graphical abstract

      Precise estimates of properties such as surface roughness, height, electrical characteristics and surface potential are obtained from scanning probe microscopy images by means of a quantitative approach based on histogram analysis (see picture).

SEARCH

SEARCH BY CITATION