Physical chemistry articles within Nature Communications

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  • Article |

    Fluorescent organic nanoparticles are attractive alternatives to quantum dots for imaging applications. Here, the authors assemble dyes with bulky counterions inside polymer nanoparticles to achieve high fluorescence brightness, as well as a photoinducible and reversible on/off switching.

    • Andreas Reisch
    • , Pascal Didier
    •  & Andrey S. Klymchenko

  • Article |

    Roaming dynamics have been shown to be important in unimolecular decompositions, but the relevance to bimolecular reactions has been less clear. Here, the authors study radical addition/elimination reactions and implicate a roaming transition state in a bimolecular reaction.

    • Baptiste Joalland
    • , Yuanyuan Shi
    •  & Alexander M. Mebel

  • Article |

    The surface chemistry of aqueous solutions plays a ubiquitous role in many chemical and biological processes. Here, the authors probe the surfaces of sodium halide solutions with surface-specific femtosecond vibrational spectroscopy, and observe surface concentrations of halide ions several times greater than in the bulk.

    • Lukasz Piatkowski
    • , Zhen Zhang
    •  & Mischa Bonn

  • Article |

    Materials with variable and reversible thermal conductivities are important in technologies, and yet such materials are rare. Here, Cho et al. report in situmeasurements of thermal conductivity of lithium cobalt oxide, and show how to reversibly modulate thermal conductivities over a considerable range.

    • Jiung Cho
    • , Mark D. Losego
    •  & Paul V. Braun

  • Article |

    The mechanical properties of small volumes are often studied but rarely are the effects of surface oxidation considered. Here, the authors perform a simulation of an aluminium nanowire with an oxide shell deforming in oxygen, finding that the oxide demonstrates superplastic deformation under load.

    • Fatih G. Sen
    • , Ahmet T. Alpas
    •  & Yue Qi

  • Article |

    The complication of water adsorption on surfaces goes well beyond a simple hexagonal bilayer model predicted by the ice rule. Chen et al.observe an extended cyclical pattern of water tetramers on an insulator surface, which is attributable to the formation of periodic Bjerrum defects at high density.

    • Ji Chen
    • , Jing Guo
    •  & En-Ge Wang

  • Article
    | Open Access

    Hydrogen bonding is an important force in nature, directing and controlling the assembly of numerous natural and synthetic structures. Here the authors show that the interpretation of intermolecular contrast in atomic force microscope images of hydrogen-bonded assemblies necessitates detailed consideration of the coupled tip-molecule system.

    • A. M. Sweetman
    • , S. P. Jarvis
    •  & P. Moriarty

  • Article |

    Thermoelectric devices can convert low-grade heat sources into electricity, but suffer from low efficiency. Here, Lee et al.present a thermally regenerative electrochemical device with copper hexacyanoferrate electrode material, which enables efficient heat-to-electricity energy conversion.

    • Seok Woo Lee
    • , Yuan Yang
    •  & Yi Cui

  • Article |

    Interactions between anions and π-systems are possible with electron-poor aromatic surfaces. Here the authors show that anion-π interactions can stabilize enolates—lowering the pKa of the carbonyl compound by almost two units—and likewise accelerate the addition of enolates to electrophiles.

    • Yingjie Zhao
    • , Naomi Sakai
    •  & Stefan Matile

  • Article |

    Cold laser material processing has relied on the use of high-peak-power lasers in order to reach the universal threshold for plasma formation of ~1 J cm−2in most solids. Here, the authors show a cold ablation process that takes off below both the threshold for plasma formation and that of the melting point of alkali halides.

    • Masaki Hada
    • , Dongfang Zhang
    •  & R.J. Dwayne Miller

  • Article |

    Desorption kinetics cannot be simply described by the standard method, the temperature-programmed desorption. Here, Günther et al.use low-energy electron microscopy to image an adsorbate layer during desorption, and propose a model that quantitatively explains the complex desorption process.

    • S. Günther
    • , T. O. Menteş
    •  & J. Wintterlin

  • Article |

    Interdigitation between polymer brushes decorated on two sliding surfaces induces low friction, which needs to be minimized for bio-lubricant applications. Here the authors show that this friction can be substantially reduced in the systems where immiscible polymer brushes are in contact.

    • Sissi de Beer
    • , Edit Kutnyanszky
    •  & Martin H. Müser

  • Article
    | Open Access

    Due to the delocalization of molecular orbitals, valence-shell spectroscopy does not allow distinction between individual atoms. Here, the authors show that for photoionization, the difference in mass—and hence recoil momentum—between atoms in a diatomic molecule allows site-selective emission to be observed.

    • Catalin Miron
    • , Quan Miao
    •  & Faris Gel'mukhanov

  • Article |

    Attempts have been made in flowing liquids over carbon nanomaterials to generate electric voltages, but a convincing or significant voltage is yet to be obtained. Here, Yin et al.show an electrokinetic process in which an electric potential of 0.1 V is generated in graphene by a moving liquid–gas boundary.

    • Jun Yin
    • , Zhuhua Zhang
    •  & Wanlin Guo

  • Article
    | Open Access

    Droplet chemistry is less susceptible to channel-fouling than single-phase flow chemistry, but is largely limited to simple reactions where all reagents are preloaded into droplets. Here, the authors report a method for multistep chemistry in droplets, using two immiscible liquids and a gas to achieve controlled, sequential reagent addition.

    • Adrian M. Nightingale
    • , Thomas W. Phillips
    •  & John C. de Mello

  • Article
    | Open Access

    Chiral determination of vapours is possible in biological systems as an important part of the olfactory system. Here, the authors describe a system that is capable of visually detecting and distinguishing the chirality of vapour-phase molecules by structural changes in a liquid crystal confined in open microchannels.

    • Takuya Ohzono
    • , Takahiro Yamamoto
    •  & Jun-ichi Fukuda

  • Article |

    It is difficult to spatially resolve molecular orbitals of molecules on highly reactive semiconductor surfaces. Here, Xu et al.use scanning tunnelling microscopy to study pyridazine molecules on a clean germanium surface, and hybridized molecular orbitals are directly imaged.

    • Jing Hui He
    • , Wei Mao
    •  & Eng Soon Tok

  • Article |

    Typically for surface adsorption there is a direct relationship between interaction strength and geometric distance—a stronger interaction leads to a shorter distance between interacting objects. Here the authors show a case where a stronger interaction leads to a larger distance, and explain this apparent paradox.

    • Benjamin Stadtmüller
    • , Daniel Lüftner
    •  & Christian Kumpf

  • Article
    | Open Access

    The oxidation state of hydride ions in oxide hosts is a matter of debate. Here, the authors address this question with a range of techniques and suggest that the electron density near an incorporated hydride ion is less than that at the hydrogen in a hydroxide ion, contrary to formal valence arguments.

    • Katsuro Hayashi
    • , Peter V. Sushko
    •  & Hideo Hosono

  • Article
    | Open Access

    Studying the high pressure phase diagram of hydrogen experimentally or by simulations presents significant challenges. Here, the authors apply a combined molecular dynamics and many-body quantum Monte Carlo approach, finding that the molecular liquid phase is stable at higher pressures than previously believed.

    • Guglielmo Mazzola
    • , Seiji Yunoki
    •  & Sandro Sorella

  • Article |

    Colloidal particles may experience a long-range force because of the confinement of solvent fluctuations. Gnan et al.show numerically that such Casimir-like effect also occurs when colloids are immersed in a chemical sol close to percolation, which provides an alternative way to tune colloidal interactions.

    • Nicoletta Gnan
    • , Emanuela Zaccarelli
    •  & Francesco Sciortino

  • Article |

    Isotopic substitution alters the optoelectronic properties of conducting polymers, but a microscopic understanding is still missing. Shao et al.address this effect using a series of polymer isotopes that are synthesized with deuterium atoms substituted either on their backbone or side chains.

    • Ming Shao
    • , Jong Keum
    •  & Kai Xiao

  • Article |

    Typically dispersion forces are weak interactions, and host–guest chemistry is dominated by more powerful events such as hydrogen bonding. Here, the authors show extremely high binding between a modified marine peptide and chloroform, driven by dispersion interactions with the chlorine atoms.

    • Gebhard Haberhauer
    • , Áron Pintér
    •  & Sascha Woitschetzki

  • Article |

    Solid contacts on a microscopic level are widely described by a classical contact mechanics theory. Here Styleet al.show that this theory breaks down when a small particle adheres to a soft surface where a fluid-like behaviour is observed because of the predominant role played by surface tension.

    • Robert W. Style
    • , Callen Hyland
    •  & Eric R. Dufresne

  • Article |

    Understanding the anisotropic electronic structure of lanthanide complexes is useful for a range of advanced applications. Here, the authors present a simple electrostatic method, capable of predicting the magnetic anisotropy of low-symmetry mononuclear and polynuclear dysprosium(III) complexes.

    • Nicholas F. Chilton
    • , David Collison
    •  & Alessandro Soncini

  • Article |

    In chemical reactions, inner barriers, which precede the rate-determining transition state, are kinetically invisible but mechanistically significant. On an example of reduction of macrocyclic disulphides, the authors quantify these inner barriers by studying the reaction rate as a function of applied force.

    • Yancong Tian
    • , Timothy J. Kucharski
    •  & Roman Boulatov

  • Article |

    Methane is a major constituent of planetary interiors, yet phase relations in the C–H system are poorly understood. This work documents the chemical reactivity of the C–H system over a wide range of temperatures and pressures, and sheds light on the chemical composition of Earth and icy giants.

    • Sergey S. Lobanov
    • , Pei-Nan Chen
    •  & Alexander F. Goncharov

  • Article |

    Membrane-less electrochemical systems eliminate the need for costly ion-exchange membranes, but typically suffer from low-power densities. Braff et al.propose a hydrogen bromine laminar flow battery, which rivals the performance of the best membrane-based systems.

    • William A. Braff
    • , Martin Z. Bazant
    •  & Cullen R. Buie

  • Article
    | Open Access

    Electrically insulating ligands and doping of colloidal semiconductor nanocrystals continue to be significant challenges for practical nanocrystal-based optoelectronics. Wheeler et al.demonstrate a new surface chemistry technique that confronts both of these challenges simultaneously.

    • Lance M. Wheeler
    • , Nathan R. Neale
    •  & Uwe R. Kortshagen

  • Article |

    Ultrafast laser pulses are useful to study electron dynamics in chemical bonds, but their influence on bond breaking is not fully understood. Wu et al. study H2 bond breaking with coincidence techniques, and find a phase-dependent anisotropy of the H+fragmentation even for isotropic multicycle laser pulses.

    • J. Wu
    • , M. Magrakvelidze
    •  & R. Dörner

  • Article
    | Open Access

    Many interesting chemical problems like photosynthesis and photovoltaics involve non-adiabatic dynamical phenomena, which are difficult to predict theoretically. Here, the authors develop a new numerical method capable of recovering quantum interferences that are neglected by conventional methods.

    • Vyacheslav N. Gorshkov
    • , Sergei Tretiak
    •  & Dmitry Mozyrsky

  • Article |

    The final state of self-assembled systems is determined by both their thermodynamic and kinetic pathways. Di Michele et al.develop a strategy to realize predesigned amorphous structures of complex DNA colloidal mixtures by selectively activating local inter- or intra-species interactions upon freezing.

    • Lorenzo Di Michele
    • , Francesco Varrato
    •  & Erika Eiser

  • Article
    | Open Access

    Nonvolatile luminescent liquids are solvent-free fluids with a range of flexible electronic applications. Here, the authors show that anthracenes enveloped in branched aliphatic compounds are stable emissive liquids, with emissive and thermoresponsive properties that may be tuned by addition of dopants.

    • Sukumaran Santhosh Babu
    • , Martin J. Hollamby
    •  & Takashi Nakanishi

  • Article |

    Noble metallic subnanometre clusters exhibit superior catalytic activities, but their stability remains a problem. Zhang et al. report that single niobium atoms can be stabilized in graphitic layers and the resulting carbide complex exhibits higher activity compared with commercial platinum nanoclusters.

    • Xuefeng Zhang
    • , Junjie Guo
    •  & Matthew F. Chisholm

  • Article |

    Classical theory predicts that glass dynamics exhibit a singularity at some finite temperature. Zhao et al. test this theory in fossil amber by determining upper bounds of the equilibrium relaxation times, and find no such behaviour even far below the glass transition challenging conventional assumptions.

    • Jing Zhao
    • , Sindee L. Simon
    •  & Gregory B. McKenna

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