Cover image for Vol. 7 Issue 6

June 12, 2006

Volume 7, Issue 6

Pages 1157–1390

    1. Cover Picture: High Density Amorphous Ice from Cubic Ice (ChemPhysChem 6/2006) (page 1157)

      Thomas Loerting, Ingrid Kohl, Werner Schustereder, Katrin Winkel and Erwin Mayer

      Version of Record online: 31 MAY 2006 | DOI: 10.1002/cphc.200690018

      The cover picture shows two powder X-ray diffractograms recorded from two different "ice" samples obtained by pressurizing cubic (red) and hexagonal (black) ice crystals at ≈80 K. Sharp peaks marked with an asterisk are from traces of hexagonal ice. In their Communication on page 1203 Loerting et al. demonstrate that the two types of ice I obtainable at ambient pressure result in two different structural states of high density amorphous ice (HDA) when pressurized to 1.5 GPa at 77 K. The background image is a high-resolution photograph of a hexagonal snowflake provided by Professor Kenneth G. Libbrecht (California Institute of Technology).

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      Enhanced Molecular Multipole Moments and Solvent Structure in Supercritical Carbon Dioxide (page 1167)

      Moumita Saharay and Sundaram Balasubramanian

      Version of Record online: 31 MAY 2006 | DOI: 10.1002/cphc.200690020

      This article corrects:

      Enhanced Molecular Multipole Moments and Solvent Structure in Supercritical Carbon Dioxide

      Vol. 5, Issue 9, 1442–1445, Version of Record online: 17 SEP 2004

    3. Passion for Precision (Nobel Lecture) (pages 1170–1187)

      Theodor W. Hänsch

      Version of Record online: 25 APR 2006 | DOI: 10.1002/cphc.200600195

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      The Nobel Prize in Physics 2005 is awarded to three scientists in the field of optics. Roy Glauber is awarded half of the Prize for his theoretical description of the behavior of light particles. John Hall and Theodor Hänsch share the other half of the Prize for their development of laser-based precision spectroscopy, including the optical frequency comb technique (see picture).

      Corrected by:

      Corrigendum: Passion for Precision (Nobel Lecture)

      Vol. 7, Issue 7, 1402, Version of Record online: 30 JUN 2006

    4. Detection of Single Oxygen Molecules Opens Up New Vistas for the Investigation of Molecular Cooperativity in Hemocyanins (pages 1189–1191)

      Philip Tinnefeld

      Version of Record online: 4 MAY 2006 | DOI: 10.1002/cphc.200600101

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      A single-molecule oxygen sensor based on fluorescence resonance energy transfer between a fluorescence dye and the respiratory protein hemocyanin is highlighted. The developed sensor offers the possibility to investigate the cooperativity of oxygen binding at the single-molecule level. The picture shows smoothed fluorescence images of the labeled 24-mer tarantula hemocyanin in the deoxygenated and oxygenated state.

    5. Electronic Conduction in the Chiral Nematic Phase of an Oligothiophene Derivative (pages 1193–1197)

      Masahiro Funahashi and Nobuyuki Tamaoki

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/cphc.200500712

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      Carrier transport characteristics in the chiral nematic phase of 2-[5-(4-[(S)-2-methylbutoxy]phenyl)-3-methyl]-2′′′-propyl-2:5′-2′:5′′-2′′:5′′′-quaterthiophene, a liquid-crystalline semiconductor (see picture), are determined with a time-of-flight technique. A non-dispersive transient photocurrent is observed in the chiral nematic phase which is attributed to an electronic processes.

    6. High-Silica Ferrierite Zeolite Self-Transformed from Aluminosilicate Gel (pages 1198–1202)

      Xiaowei Cheng, Jing Wang, Juan Guo, Jun Sun and Yingcai Long

      Version of Record online: 4 MAY 2006 | DOI: 10.1002/cphc.200600002

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      Perfectly built zeolites: Ferrierite (FER) zeolite, with the perfect crystal structure and the same preferential orientation as siliceous FER zeolite, is synthesized by the self transformation of the amorphous seeded dry gel with a novel vapor phase transport (VPT) method in the mixed vapor of tetrahydrofuran and water.

    7. High Density Amorphous Ice from Cubic Ice (pages 1203–1206)

      Thomas Loerting, Ingrid Kohl, Werner Schustereder, Katrin Winkel and Erwin Mayer

      Version of Record online: 4 MAY 2006 | DOI: 10.1002/cphc.200600011

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      Cooler than ice: The structural and thermodynamic properties of high-density amorphous ice (HDA) prepared from two different starting materials, cubic ice and hexagonal ice, are compared. The resulting HDA states, have similar densities, however as shown by X-ray structure factors (see figure) and differential scanning calorimetry, they differ in structure and enthalpy.

    8. Thermal Expansion of Microstructured DMPC Bilayers Quantified by Temperature-Controlled Atomic Force Microscopy (pages 1207–1210)

      Steffen Schuy and Andreas Janshoff

      Version of Record online: 5 MAY 2006 | DOI: 10.1002/cphc.200600013

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      Microcalorimetry of single bilayers: Temperature-controlled AFM (see images; DMPC=1,2-dimyristoyl-sn-glycero-3-phospocholine) of microstructured lipid bilayers allows for the exact determination of the main phase transition temperature of solid supported membranes. The authors show that changes in membrane thickness, thermal expansion and boundary fluctuations can be determined simultaneously as a function of temperature.

    9. A Parameter-Free Quantum-Mechanical Approach for Calculating Electron-Transfer Rates for Large Systems in Solution (pages 1211–1214)

      Roberto Improta, Vincenzo Barone and Marshall D. Newton

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/cphc.200600069

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      You shall know their velocity: On the grounds of the Marcus theory, and exploiting the recent advances of quantum-mechanical methods, the authors prove that it is possible to accurately compute the rate constants for dissociative electron transfer in large systems directly in the condensed phase (see figure).

    10. Vibrational Frequencies of Water Adsorbed on (111) and (221) Nickel Surfaces from First Principle Calculations (pages 1215–1219)

      Tatiana Murakhtina, Luigi Delle Site and Daniel Sebastiani

      Version of Record online: 3 MAY 2006 | DOI: 10.1002/cphc.200500642

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      Good vibrations: Water molecules adsorbed on transition metal surfaces undergo significant changes in their vibrational modes and frequencies (see figure). The authors use ab initio calculations to rationalize IR peaks as a function of adsorption sites and cluster sizes, enabling for the first time a direct comparison of measurements and calculations.

    11. Car–Parrinello Molecular Dynamics Study of the Blue-Shifted F3CH⋅⋅⋅FCD3 System in Liquid N2 (pages 1221–1228)

      Pawel Rodziewicz, Konstanty S. Rutkowski, Sonia M. Melikova, Aleksander Koll and Francesco Buda

      Version of Record online: 15 MAY 2006 | DOI: 10.1002/cphc.200600061

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      Into the blue: The dynamic conformational changes of the hydrogen-bonded complex formed by fluoroform and deuterated methyl fluoride in liquid nitrogen are examined on the basis of Car–Parrinello molecular dynamics (see picture). Vibrational analysis reproduces the blue shift of the fundamental stretching frequency ν(C[BOND]H). The spectroscopic parameters and residence times of particular structures of the F3CH/FCD3 complex are also derived.

    12. Ab Initio Molecular Dynamics Study of the Keto–Enol Tautomerism of Acetone in Solution (pages 1229–1234)

      Clotilde S. Cucinotta , Alice Ruini , Alessandra Catellani  and András Stirling

      Version of Record online: 9 MAY 2006 | DOI: 10.1002/cphc.200600007

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      It only takes one: The barrier for the tautomerism of acetone is significantly reduced by one H2O molecule which allows a more favorable conformation for the double-bond shift and participates in the proton transfer. When surrounded by many water molecules, acetone enjoys an even more favorable environment for keto–enol rearrangements, as demonstrated by ab initio molecular dynamics simulation (see picture).

    13. Spectroscopic and Theoretical Studies of Optically Active Porphyrin Dimers: A System Uninterpretable by Exciton Coupling Theory (pages 1235–1240)

      Atsuya Muranaka, Yoshiaki Asano, Akihiko Tsuda, Atsuhiro Osuka and Nagao Kobayashi

      Version of Record online: 3 MAY 2006 | DOI: 10.1002/cphc.200500611

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      Coupled chiral complexes: The helical configuration of a mesomeso β–β doubly linked bis-porphyrin molecule is reassigned as right-handed (see picture) by inspection of the experimental spectroscopic properties in conjunction with time-dependent DFT calculations. This assignment is contrary to that previously reported on the basis of the exciton chirality method.

    14. Determining the Intermolecular Structure in the S0 and S1 States of the Phenol Dimer by Rotationally Resolved Electronic Spectroscopy (pages 1241–1249)

      Michael Schmitt, Marcel Böhm, Christian Ratzer, Daniel Krügler, Karl Kleinermanns, Ivo Kalkman, Giel Berden and W. Leo Meerts

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/cphc.200500670

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      Excited state structures: The intermolecular geometry of the phenol dimer is determined from the rotationally resolved UV spectra of five isotopomers. The spectra are analyzed by a fitting strategy based on a genetic algorithm. The authors find that the electronic ground state has a longer hydrogen bond and a smaller tilt angle between the aromatic rings than the excited state (see picture).

    15. A Crossed Molecular Beam Imaging Study of the O(1D2)+HCl[RIGHTWARDS ARROW]OH+Cl(2PJ=3/2, 1/2) Reaction (pages 1250–1257)

      Hiroshi Kohguchi and Toshinori Suzuki

      Version of Record online: 31 MAY 2006 | DOI: 10.1002/cphc.200500650

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      Cross-examination: The reaction of atomic oxygen in the first excited singlet state [O(1D2)] with HCl is studied by crossed molecular beam scattering at a collision energy of 6 kcal mol−1 [see scattering images with superimposed Newton diagram in (a)]. State-resolved doubly differential cross sections (DCSs) are obtained for Cl(2P3/2) and Cl*(2P1/2) products by velocity-map ion imaging. Both products are slightly more forward scattered.

    16. Low-Temperature EPR and Mössbauer Spectroscopy of Two Cytochromes with His–Met Axial Coordination Exhibiting HALS Signals (pages 1258–1267)

      Giorgio Zoppellaro, Thomas Teschner, Espen Harbitz, Volker Schünemann, Solveig Karlsen, David M. Arciero, Stefano Ciurli, Alfred X. Trautwein, Alan B. Hooper and K. Kristoffer Andersson

      Version of Record online: 10 MAY 2006 | DOI: 10.1002/cphc.200500693

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      Taking a closer look: Although structurally very similar (see figure), cytochromes c552 and c553 feature differences in their relative percentage of axial and rhombic components, as judged by electron paramagnetic resonance and Mössbauer spectroscopy analyses.

    17. Experimental and Theoretical Study of 2,6-Difluorophenylnitrene, Its Radical Cation, and Their Rearrangement Products in Argon Matrices (pages 1268–1275)

      Claudio Carra, Rafael Nussbaum and Thomas Bally

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/cphc.200600043

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      Radical rearrangements: 2,6-Difluorophenylnitrene can be selectively and completely transformed into its two isomers, the bicyclic azirine and the cyclic ketenimine, by light of suitable wavelengths (see picture). All three isomers are ionized in Ar matrices, but only two cationic isomers are formed: the radical cations of the phenylnitrene and the cyclic ketenimine. The latter is an aromatic species akin to the tropylium cation.

    18. Raman Spectroscopy of Short-Lived Terthiophene Radical Cations Generated by Photochemical and Chemical Oxidation (pages 1276–1285)

      Tracey M. Clarke, Keith C. Gordon, Wing Sum Chan, David Lee Phillips, Pawel Wagner and David L. Officer

      Version of Record online: 4 MAY 2006 | DOI: 10.1002/cphc.200500680

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      Radical cations: Transient Raman spectroscopy is employed to capture the spectral signatures from very reactive short-lived terthiophene radical cation species (see lowest unoccupied molecular orbital of 3′-[(E)-2-(4-nitrophenyl)ethenyl]-2,2′:5′,2′′-terthiophene radical cation). The spectra of these radical cations show characteristic intense bands in the low-frequency region that are assigned to C[BOND]S stretching modes.

    19. Spin-Density Distribution in the Copper Site of Azurin (pages 1286–1293)

      Maria Fittipaldi, Gertrud C. M Warmerdam, Ellen C. de Waal, Gerard W. Canters, Davide Cavazzini, Gian Luigi Rossi, Martina Huber and Edgar J. J. Groenen

      Version of Record online: 9 MAY 2006 | DOI: 10.1002/cphc.200500551

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      A pulsed deuterium ENDOR study is performed at 95 GHz on single crystals of azurin (see picture) from Pseudomonas aeruginosa selectively deuterated at the Cβ position of copper-coordinating cysteine 112. Complete hyperfine tensors of the two deuterium atoms obtained, reveal identical isotropic parts. From the analysis of the hyperfine tensors ≈45 % of the spin density in the paramagnetic site is attributed to copper and 30 % to sulfur.

    20. Hartree–Fock Energy Partitioning in Terms of Hirshfeld Atoms (pages 1294–1305)

      Marcos Mandado, Christian Van Alsenoy, Paul Geerlings, Frank De Proft and Ricardo A. Mosquera

      Version of Record online: 15 MAY 2006 | DOI: 10.1002/cphc.200500606

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      Atomic energy: Total molecular energy can be decomposed into atomic energies by a method based on a Hirshfeld atomic partitioning scheme. The calculated atomic energies describe atoms in a large series of molecules, and are dependent on the electron population and atomic hybridization. The graph shows the diagonal term of the atomic energy (E) versus the atomic electron population (N) for hydrogen (χ=electronegativity).

    21. Influence of Cluster Size on the Structures and Stability of Trimetallic Nitride Fullerenes M3N@C80 (pages 1306–1310)

      Li-Hua Gan and Ruo Yuan

      Version of Record online: 4 MAY 2006 | DOI: 10.1002/cphc.200500666

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      Influential interactions: Density functional calculations performed on M3N@C80 (M=Sc, Y, La) show that the M–cage and M—M interactions determine cluster geometries and stability; Sc3N (left) and Y3N (central) are planar, whereas La3N (right) is pyramidal inside C80-Ih. The interior of C80-Ih is large enough to allow the rotation of the Sc3N cluster but not of the Y3N and La3N clusters.

    22. Density Functional Study of Methyl Chemisorption on Polycyclic Aromatic Hydrocarbons (pages 1311–1321)

      Barbara V. Unterreiner, Yannick Carissan and Wim Klopper

      Version of Record online: 3 MAY 2006 | DOI: 10.1002/cphc.200500673

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      Functional features: The chemisorption of methyl radicals (• in the figure) at different positions on large (up to C96H24 ) polycyclic aromatic hydrocarbons (PAHs) are theoretically studied using four density functionals. The equilibrium and transition structures are determined and the relative energies are rationalized by Hückel molecular orbital (HMO) theory.

    23. Mapping Electrochemiluminescence as Generated at Double-Band Microelectrodes by Confocal Microscopy under Steady State (pages 1322–1327)

      Christian Amatore, Cécile Pebay, Laurent Servant, Néso Sojic, Sabine Szunerits and Laurent Thouin

      Version of Record online: 4 MAY 2006 | DOI: 10.1002/cphc.200500626

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      Confined light emission: A confocal microspectrometer is used to monitor electrochemiluminescence (ECL) produced by the annihilation reaction between Ru(bpy)3+ and Ru(bpy)33+ (see scheme). Each species is electrochemically generated at one electrode of a double-band microelectrode assembly leading to ECL emission in the interelectrode gap.

    24. The Theory of Non-Cottrellian Diffusion on the Surface of a Sphere or Truncated Sphere (pages 1328–1336)

      Mary Thompson, Gregory G. Wildgoose and Richard G. Compton

      Version of Record online: 3 MAY 2006 | DOI: 10.1002/cphc.200500687

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      Spherical diffusion of charge: Microparticles surface-modified with electroactive material are immobilised onto an electrode surface and the spherical charge diffusion in the limit of reversible electrode kinetics is modelled (see figure). The authors extend the theory to model truncated spheres on electrode surfaces; a range of results is observed, with Cottrell-like behaviour seen only for more truncated particles.

    25. Oxygenated Edge Plane Sites Slow the Electron Transfer of the Ferro-/Ferricyanide Redox Couple at Graphite Electrodes (pages 1337–1344)

      Xiaobo Ji, Craig E. Banks, Alison Crossley and Richard G. Compton

      Version of Record online: 3 MAY 2006 | DOI: 10.1002/cphc.200600098

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      Aerial oxidation: The oxidation effects on the electron transfer kinetics of ferrocyanide, potassium hexachloroiridate(III), hexaammineruthenium(III) chloride, and N,N,N′,N′-tetramethyl-p-phenylenediamine are explored by leaving freshly prepared basal plane and edge plane pyrolytic graphite electrodes in air for various periods of time. Oxygenated species decrease the electron transfer kinetics of ferrocyanide (see voltammograms).

    26. Theoretical Investigation of the Decarbonylation of Acetaldehyde by Fe+ and Cr+ (pages 1345–1354)

      Lianming Zhao, Wenyue Guo, Rongrong Zhang, Shujuan Wu and Xiaoqing Lu

      Version of Record online: 3 MAY 2006 | DOI: 10.1002/cphc.200500720

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      Transition-metal ion strategies: A theoretical investigation is performed to elucidate the mechanism of Cr+- and Fe+-mediated decarbonylation of acetaldehyde. The process occurs via a sextet potential energy surface (PES) for Cr+, whereas for Fe+, decarbonylation occurs on both quartet and sextet PESs and spin–orbit coupling (SOC) enables the ground-state reactants to crossover to the energetically preferable quartet pathway (see figure).

    27. Effects of Polymer Architecture and Composition on the Adhesion of Poly(tetrafluoroethylene) (pages 1355–1360)

      Chen-Yuan Tu, Ying-Ling Liu, Min-Tzu Luo, Kueir-Rarn Lee and Juin-Yih Lai

      Version of Record online: 10 MAY 2006 | DOI: 10.1002/cphc.200500729

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      Enhancing adhesion: PTFE [poly(tetrafluoroethylene)]-copper adhesion increases when arborescent PGMA [poly(glycidyl methacrylate)] is incorporated onto the surface of PTFE. The authors show that epoxide ring-opening reactions of the PGMA groups (see picture) result in polar hydroxyl groups which further improve the adhesion.

    28. Membrane Binding and Structure of De Novo Designed α-Helical Cationic Coiled-Coil-Forming Peptides (pages 1361–1371)

      Toni Vagt, Olaf Zschörnig, Daniel Huster and Beate Koksch

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/cphc.200600010

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      Looping the loop: The secondary structure of cationic coiled-coil peptides in the membrane-bound state is studied in the presence of negatively charged lipid membranes (see picture). The phospholipids have a strong effect on the peptide structure and the induction of vesicle aggregation because of this interaction. However, neither membrane leakage nor fusion was detected upon peptide binding, which is unusual for amphiphatic peptide structures.

    29. Femtosecond Dynamics on 2-(2′-Hydroxy-4′-diethylaminophenyl)benzothiazole: Solvent Polarity in the Excited-State Proton Transfer (pages 1372–1381)

      Yi-Ming Cheng, Shih-Chieh Pu, Chia-Jung Hsu, Chin-Hung Lai and Pi-Tai Chou

      Version of Record online: 25 APR 2006 | DOI: 10.1002/cphc.200600017

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      Dynamic dipoles: Upon Franck–Condon (FC) excitation, 2-(2′-hydroxy-4′-diethylaminophenyl)benzothiazole (HABT) undergoes excited-state intramolecular proton transfer (ESIPT) and solvation relaxation processes concurrently. In the equilibrium configurations Neq* and Teq*, forward and/or backward ESIPT occurs with an appreciable solvent-polarity-induced barrier due to differences in polarization equilibrium between Neq* and Teq* (see picture).

    30. Gas-Phase Spectroscopy of the Unstable Sulfur Diisocyanate Molecule S(NCO)2 (pages 1382–1387)

      Weigang Wang , Maofa Ge, Li Yao , Xiaoqing Zeng , Zheng Sun and Dianxun Wang

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/cphc.200600084

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      Characterization accomplished: The electronic structure of sulfur diisocyanate is characterized by photoelectron spectroscopy. The ionization and dissociation pathways (see figure) are discussed and in combination with calculated bond dissociation energies, the authors show that a 1,3–sigmatropic rearrangement occurs prior to the formation of the dissociation products OCNCO+ and NS+.

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      Preview: ChemPhysChem 6/2006 (page 1390)

      Version of Record online: 31 MAY 2006 | DOI: 10.1002/cphc.200690021