Physical chemistry articles within Nature Chemistry

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  • Article |

    Histone H1 binds to nucleosomes with ultrahigh affinity, implying residence times incompatible with efficient biological regulation. Now it has been shown that the disordered regions of H1 retain their large-amplitude dynamics on the nucleosome, which enables a charged disordered histone chaperone to invade the H1–nucleosome complex and vastly accelerate H1 dissociation.

    • Pétur O. Heidarsson
    • , Davide Mercadante
    •  & Benjamin Schuler

  • News & Views |

    Why do bulky anions solubilize macromolecules in water but precipitate out the corresponding monomers? The answer lies in the differences in local water structure. Polymers have now been shown to disrupt water structure more than their monomers, leading to an accumulation of anions near the polymers that increases their solubility.

    • Aniket U. Thosar
    •  & Amish J. Patel

  • Article |

    Aromatic systems that interact non-covalently are important in many settings, such as base-pair stacking and DNA–drug interactions; however, their excited-state molecular dynamics are not fully understood. Now, intermolecular Coulombic decay in benzene dimers has been observed. The process is initiated by electron-impact ionization and proceeds through ultrafast energy transfer between the benzene molecules.

    • Xueguang Ren
    • , Jiaqi Zhou
    •  & Alexander Dorn

  • Article
    | Open Access

    Complex coacervate microdroplets have been proposed as primordial cells, but their ability to evolve by fusion, growth and fission has not yet been demonstrated. Now, it has been shown that gas bubbles inside heated rock pores can drive the growth, fusion, division and selection of coacervate microdroplets.

    • Alan Ianeselli
    • , Damla Tetiker
    •  & T.-Y. Dora Tang

  • News & Views |

    Atmospheric chemists have been unable to explain the rapid sulfate formation observed during wintertime aerosol pollution events. Now, kinetic measurements in atmospherically relevant aerosol particles have highlighted a significant role for nitrogen dioxide in sulfate formation via its interfacial reaction with dissolved SO2.

    • Jian Zhen Yu

  • Article |

    Electron spin resonance spectroscopy has traditionally been used to study large ensembles of spins, but its combination with scanning tunnelling microscopy recently enabled measurements on single adatoms. Now, individual iron phthalocyanine complexes adsorbed on a surface have been probed. Their spin distribution partially extends on the phthalocyanine, leading to a strong geometry-dependent exchange coupling interaction.

    • Xue Zhang
    • , Christoph Wolf
    •  & Taeyoung Choi

  • Article |

    Weakly hydrated anions solubilize macromolecules but cause small molecules that are made from identical chemical constituents to precipitate out of aqueous solutions. Now, this phenomenon has been understood by demonstrating that the binding of anions to polymers is regulated by molecular curvature and interfacial water structure.

    • Bradley A. Rogers
    • , Halil I. Okur
    •  & Paul S. Cremer

  • News & Views |

    Machine learning algorithms are fast surpassing human abilities in multiple tasks, from image recognition to medical diagnostics. Now, machine learning algorithms have been shown to be capable of accurately predicting the folded structures of proteins.

    • Cecilia Clementi

  • Article |

    Self-propelled artificial chemical swimmers have previously been developed for chemical sensing. Now, hybrid bioelectrochemical swimmers, capable of translating chiral molecular information into macroscopic motion, have been developed. Diastereomeric interactions between enantiopure oligomers immobilized on the swimmer and a chiral molecule present in solution control the trajectory of the device.

    • Serena Arnaboldi
    • , Gerardo Salinas
    •  & Alexander Kuhn

  • Article |

    The use of anionic redox chemistry in high-capacity Li-rich cathodes is being hampered by voltage hysteresis, the origin of which remains obscure. Now it has been shown that sluggish ligand-to-metal charge transfer kinetically traps an intermediate Fe4+ species and is responsible for voltage hysteresis in the prototypical Li-rich cation-disordered rock-salt Li1.17Ti0.33Fe0.5O2.

    • Biao Li
    • , Moulay Tahar Sougrati
    •  & Jean-Marie Tarascon

  • News & Views |

    Transition metal complexes with metal-to-ligand charge transfer (MLCT) luminescence and photoactivity typically rely on precious metals such as ruthenium or iridium. Now, two complexes of the Earth-abundant 3d manganese have displayed room-temperature MLCT luminescence in solution and a unique excited-state reactivity.

    • Katja Heinze

  • News & Views |

    Charged nanoparticles can behave as large ions or as small colloids. Their interaction with multivalent ions has now been shown to reflect this dichotomy, providing new paths to large, self-assembled nanoparticle superstructures.

    • Tobias Kraus

  • Article
    | Open Access

    The breakdown of the Born–Oppenheimer approximation is omnipresent in chemistry and detailed understanding of non-adiabatic dynamics is still incomplete. Now, the non-adiabatic quenching of electronically excited OH(A2Σ+) molecules by H2 has been investigated using full-dimensional quantum dynamics calculations and a high-quality diabatic-potential-energy matrix, providing insight into the branching ratio of the two electronic quenching channels.

    • Bin Zhao
    • , Shanyu Han
    •  & Hua Guo

  • Article |

    As the number of atoms involved in a reaction increases, so do the experimental and theoretical challenges faced when studying their dynamics. Now, using ion-imaging experiments and quasi-classical trajectory simulations, the dynamics of the polyatomic reaction F– + CH3CH2Cl have been studied and the competition between bimolecular nucleophilic substitution and base-induced elimination has been disentangled.

    • Jennifer Meyer
    • , Viktor Tajti
    •  & Roland Wester

  • Article |

    Manganese(i) is isoelectronic to iron(ii) but has typically been overlooked as a cheap Earth-abundant metal for the development of 3d6 metal-to-ligand charge transfer (MLCT) emitters and photosensitizers. Now, using chelating isocyanide ligands, air-stable manganese(i) complexes have been obtained that exhibit MLCT luminescence, as well as energy- and electron-transfer photoreactivity.

    • Patrick Herr
    • , Christoph Kerzig
    •  & Oliver S. Wenger

  • News & Views |

    Energy transfer from one molecule to another over a distance of nanometres is a fundamental process of widespread relevance. Now, scanning probe techniques have been used to include an intermediary third molecule and to watch how energy flows through it.

    • Klaus Kuhnke

  • News & Views |

    Excited anion states provide doorways for molecular electron capture. Now, two-dimensional photoelectron spectroscopy of cluster anions has been shown to be a powerful tool for revealing the role of the local environment in facilitating the process.

    • C. Annie Hart
    •  & Richard Mabbs

  • Article |

    Droplet interface bilayer measurements have now shown that membranes formed from chiral phospholipid bilayers are enantioselectively permeable to chiral amino acids. The results show that membrane stereochemistry is necessary and sufficient to drive such enantioselective transport, presenting a new potential route to homochirality. These findings could also have implications for pharmacokinetics and drug design.

    • Juan Hu
    • , Wesley G. Cochrane
    •  & Brian M. Paegel

  • Meeting Report |

    Chirality is fundamental to chemistry, molecular biology and photonics, but chirality itself is not often in the spotlight. Lewis E. MacKenzie and Patrycja Stachelek report on the 2021 Chiral Materials meeting, which explored how chirality manifests in functional materials, and how it can lead to new technological applications.

    • Lewis E. MacKenzie
    •  & Patrycja Stachelek

  • Article |

    Energy funnelling within multichromophoric assemblies is key to the conversion of solar energy by plants. Now, energy transport between phthalocyanine-based chromophores has been monitored at the submolecular level using scanning tunnelling microscopy, focusing on the role of ancillary, passive and blocking chromophores in promoting and directing energy transfer between distant donor and acceptor units.

    • Shuiyan Cao
    • , Anna Rosławska
    •  & Guillaume Schull

  • Article |

    Although electron-driven chemistry is ubiquitous, how molecular electron capture is altered by solvent remains poorly understood. Now, using anion two-dimensional photoelectron spectroscopy, it is shown that the presence of water molecules can enhance electron capture and that considering the mechanism from the perspective of the anion offers further understanding.

    • Aude Lietard
    • , Golda Mensa-Bonsu
    •  & Jan R. R. Verlet

  • News & Views |

    Controlling reactions between molecules is a major fundamental goal in chemistry and doing so on the level of individual quantum states is very challenging. Now, control over the reactant state and full characterization of the product-state distribution of an ultracold bimolecular reaction has been demonstrated.

    • Andreas Osterwalder

  • Article |

    The overall efficiency of free-triplet generation from intramolecular singlet fission is limited by the efficiency of the dissociation of spatially adjacent triplet pairs. Now, using transient magneto-optical spectroscopy, it has been shown that this limitation can be overcome by promoting a pathway mediated by spatially separated triplet pairs in tetracene trimers and tetramers.

    • Zhiwei Wang
    • , Heyuan Liu
    •  & Min Xiao

  • News & Views |

    The physical properties of a liquid at an interface differ from bulk solution limits, but how this affects chemical reactivity is unclear. Now, ultrafast, surface-sensitive vibrational spectroscopy has revealed that the light-induced reaction of phenol with water is four orders of magnitude faster at the water surface than in bulk.

    • Robert A. Walker

  • Article |

    Analysis of the thermodynamics of protein–N-glycan interactions perturbed by mutations has revealed an enthalpy–entropy compensation that depends on the electronics of the interacting side chains. Machine-learned and statistical models showed that protein–N-glycan interactions highly correlate with stereoelectronic effects, and that a major part of protein–N-glycan interactions can be explained using the energetic rules of frontier molecular orbital interactions.

    • Maziar S. Ardejani
    • , Louis Noodleman
    •  & Jeffery W. Kelly

  • Article |

    Solvent plays a critical role in electron-transfer reactions, but short-range solvation dynamics are challenging to observe. Now, femtosecond X-ray solution scattering has been used to directly monitor the reorganization of water upon ultrafast intramolecular electron transfer in a bimetallic complex. Coherent motions of the first-shell water molecules are observed, arising from changes in solute–solvent hydrogen bonding.

    • Elisa Biasin
    • , Zachary W. Fox
    •  & Munira Khalil

  • Article |

    Reactions at the interface between water and other phases play important roles in various chemical settings. Now, ultrafast phase-sensitive interface-selective vibrational spectroscopy has revealed that the photoionization of phenol can occur four orders of magnitude faster at the water surface than in the bulk aqueous phase.

    • Ryoji Kusaka
    • , Satoshi Nihonyanagi
    •  & Tahei Tahara

  • Article |

    Energy scrambling in intermediate complexes—which form in many chemical reactions—presents a major challenge to state-to-state control. However, nuclear spin tends to remain unchanged throughout reactions and now, by manipulating the reactants’ nuclear spins using an external magnetic field, control over the product state distribution of a bimolecular reaction has been demonstrated.

    • Ming-Guang Hu
    • , Yu Liu
    •  & Kang-Kuen Ni

  • Article |

    Metallocenes are attractive mechanophores because they are stable in the absence of force, yet reactive under tension. Now, covalently bridging the two cyclopentadienyl (Cp) ligands of ferrocenes embedded in a polymer has been shown to alter their mechanochemical reactivity, leading to a faster dissociation of the Fe–Cp bond, which occurs through a peeling mechanism rather than a shearing one.

    • Yudi Zhang
    • , Zi Wang
    •  & Stephen L. Craig

  • Article |

    134Ce and 134La have great potential as companion diagnostic isotopes for radiotherapeutics labelled with α-emitting 225Ac and 227Th. Now, by controlling the CeIII/CeIV redox couple, the large-scale production, purification and characterization of 134Ce- and 134La-based radiolabels has been achieved and their use for in vivo positron emission tomography is demonstrated.

    • Tyler A. Bailey
    • , Veronika Mocko
    •  & Rebecca J. Abergel

  • Article |

    Electronic–vibrational interplay can enable electron and energy transfer processes to be regulated. Now, coherence spectroscopy has been used to disentangle two vibrational pathways that control an electron transfer reaction. It has been shown that a fast, effectively ballistic, electron transfer along one vibrational path acts like a pulse to generate a coherent wavepacket along another vibrational pathway.

    • Shahnawaz R. Rather
    • , Bo Fu
    •  & Gregory D. Scholes

  • Article |

    The role of the biexcitonic triplet-pair state 1(TT) during triplet–triplet annihilation events in singlet-fission materials has been the subject of recent debate. Now, emissive 1(TT) states have been shown to be direct products of triplet–triplet annihilation in both endothermic and exothermic singlet-fission materials.

    • David G. Bossanyi
    • , Maik Matthiesen
    •  & Jenny Clark

  • Article |

    Cyanide-bridged CoFe coordination networks exhibit photomagnetism because of coupled charge-transfer and spin transition. Now, femtosecond X-ray and optical absorption spectroscopies have enabled the electronic and structural dynamics of this light-induced process to be disentangled and show that it is the spin transition on the cobalt atom, occurring within ~50 fs, that induces the Fe-to-Co charge-transfer within ~200 fs.

    • Marco Cammarata
    • , Serhane Zerdane
    •  & Eric Collet

  • Article |

    Low-temperature scattering leads to the formation of quantum resonances or quasi-bound states, which are observable as peaks in the measured collision cross-sections. Now it has been shown that two different formation mechanisms, quantum tunnelling and quantum reflection, can be distinguished by measuring and comparing elastic and inelastic scattering, which probe the spatial localization of the resonance wavefunctions.

    • Prerna Paliwal
    • , Nabanita Deb
    •  & Edvardas Narevicius

  • Article |

    Metal–organic frameworks (MOFs) can combine porosity and magnetic order within their lattice, which makes them attractive for the development of stimuli-responsive magnets. Now, a MOF has been prepared that converts from a ferrimagnet to a paramagnet with CO2 uptake, and returns to the ferrimagnetic state on releasing CO2.

    • Jun Zhang
    • , Wataru Kosaka
    •  & Hitoshi Miyasaka

  • News & Views |

    Interactions between two bodies that are both attractive and repulsive — such as predators chasing prey — are common in nature. Similar chasing behaviour has now been engineered in self-propelling microdroplets and controlled through fundamental physical and chemical mechanisms.

    • Corinna C. Maass

  • Article |

    Conducting high-resolution, multiplexed imaging in living mammals is challenging because of considerable scattering and autofluorescence in tissue at visible and near-infrared wavelengths. Now, real-time, non-invasive multicolour imaging experiments in live animals have been achieved through the design of optical contrast agents for the shortwave infrared (SWIR, 1,000–2,000 nm) region and the introduction of excitation multiplexing with single-channel SWIR detection.

    • Emily D. Cosco
    • , Anthony L. Spearman
    •  & Ellen M. Sletten

  • News & Views |

    How atoms organize during the earliest stages of nucleation has been a subject of speculation for over a century. Using atomically resolved electron microscopy, the formation and ordering of metal clusters from individual atoms has now been observed in carbon nanotubes that serve as ‘test tubes’.

    • J. J. De Yoreo
    •  & B. A. Legg

  • Article |

    High-accuracy quantum chemistry methods struggle with a combinatorial explosion of Slater determinants in larger molecular systems, but now a method has been developed that learns electronic wavefunctions with deep neural networks and reaches high accuracy with only a few determinants. The method is applicable to realistic chemical processes such as the automerization of cyclobutadiene.

    • Jan Hermann
    • , Zeno Schätzle
    •  & Frank Noé

  • Article |

    Crystal symmetry is notoriously uncorrelated to the symmetry of the constituent molecules that make up a crystal. Symmetry breaking is typically thought to occur during nucleation and growth, but a symmetry element of olanzapine crystals—an inversion centre—has now been shown to emerge in centrosymmetric dimers extant in solution prior to crystallization.

    • Monika Warzecha
    • , Lakshmanji Verma
    •  & Peter G. Vekilov

  • Article |

    Quantum machine learning with improved data efficiency and transferability has been achieved using on-the-fly selection of query-dependent training molecules, which are drawn from a ‘dictionary’ of atom-in-molecule-based fragments. The benefits of the resulting models have been demonstrated for important molecular properties and for systems including organic molecules, 2D materials, water clusters, DNA base pairs and ubiquitin.

    • Bing Huang
    •  & O. Anatole von Lilienfeld

  • Article |

    Crystal nucleation processes are difficult to probe experimentally because of the spatial and temporal scales involved. Now, the heterogeneous nucleation of three different metals has been observed by electron microscopy with atomic resolution—using single-walled carbon nanotube as test tubes—and, in each case, shown to adopt a two-step nucleation mechanism involving a metastable amorphous precursor.

    • Kecheng Cao
    • , Johannes Biskupek
    •  & Ute Kaiser

  • News & Views |

    Recent research has shown that vibronic coherences are one of the primary drivers for ultrafast light-induced processes. Now, ultrafast spectroscopy has been used to uncover vibronic coherences in the excited-state dynamics of an iron complex, leading to its redesign and the drastic prolonging of its excited-state lifetime.

    • Julia A. Weinstein

  • Article |

    Photoinduced isomerization reactions, including ring-opening reactions, lie at the heart of many chemical processes in nature. The pathway and dynamics of the ring opening of a model heterocycle have now been investigated by femtosecond photoelectron spectroscopy combined with ab initio theory, enabling the visualization of rich dynamics in both the ground and excited electronic states.

    • Shashank Pathak
    • , Lea M. Ibele
    •  & Daniel Rolles

  • News & Views |

    Is a nanoscale hydrophobic bowl wet or dry when dissolved in water? It turns out that the answer depends on the architecture of its rim. A molecular host decorated with four methyl groups around its rim pointing inward, rather than up, has now been shown to expel water from the bowl, making it dry and sticky.

    • Shekhar Garde

  • Article |

    Water plays an active role in modulating guest recognition by both artificial and biological hosts, but how this role can be controlled is unclear. Now, the de-wetting of the non-polar pockets of cavitands is shown to be affected by the orientation of methyl groups encircling the portal, which moderate the enthalpic and entropic contributions driving recognition.

    • J. Wesley Barnett
    • , Matthew R. Sullivan
    •  & Henry S. Ashbaugh

  • Article |

    Scattering experiments in which two beams nearly co-propagate allow broadly tunable collision energies and can enable cold collisions. Now, such experiments have been combined with the preparation of NO molecules using stimulated emission to generate highly vibrationally excited states for state-to-state scattering studies, testing the theoretical gold standard in a regime not found in nature.

    • Chandika Amarasinghe
    • , Hongwei Li
    •  & Arthur G. Suits

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