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| Open AccessZero-field J-spectroscopy of quadrupolar nuclei
Zero to ultralow-field NMR provides chemical information in the absence of a high magnetic field but it is difficult to measure molecules with quadrupolar nuclei due to their fast relaxation. This study examines zero-field J-spectra from isotopologues of ammonium cations, with quadrupolar nuclei, revealing the presence of a primary isotope effect of −58 mHz.
- Román Picazo-Frutos
- , Kirill F. Sheberstov
- & Danila A. Barskiy
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Article
| Open AccessReal-time observation of two distinctive non-thermalized hot electron dynamics at MXene/molecule interfaces
Photoexcited MXenes could transfer charge carriers to or heat molecules at their interfaces. Here, the authors show using time-resolved spectroscopy that the non-thermalized carriers can directly transfer to molecules or heat them within 125 fs.
- Qi Zhang
- , Wei Li
- & Xueming Yang
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| Open AccessIntermolecular interactions probed by rotational dynamics in gas-phase clusters
The authors demonstrate, using coincident Coulomb explosion imaging, that the rotational dynamics of single nitrogen molecules can be used as a probe to sense the interactions with surrounding Ar atoms in gas-phase clusters.
- Chenxu Lu
- , Long Xu
- & Jian Wu
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Article
| Open AccessHeavy-atom tunnelling in singlet oxygen deactivation predicted by instanton theory with branch-point singularities
Singlet oxygen relaxes in water to its triplet ground state. Here, the authors show that heavy-atom tunnelling speeds up this reaction from time scales longer than the age of the universe to microseconds.
- Imaad M. Ansari
- , Eric R. Heller
- & Jeremy O. Richardson
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Article
| Open AccessExplainable chemical artificial intelligence from accurate machine learning of real-space chemical descriptors
Chemical AI often behaves as a black box, providing accurate, but opaque, predictions. Here, the authors show that the synergy of cutting-edge ANNs with the rigor of Quantum Chemical Topology can result in Explainable Chemical AI (XCAI).
- Miguel Gallegos
- , Valentin Vassilev-Galindo
- & Alexandre Tkatchenko
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Article
| Open AccessReduction of precious metal ions in aqueous solutions by contact-electro-catalysis
Currently, precious metal recovery from e-waste water is usually performed by liquid extraction or sorbent processes. Here, the authors show the untapped potential of dielectric insulators as catalysts for the 1-step selective recovery of gold in aqueous solutions by contact-electrocatalysis.
- Yusen Su
- , Andy Berbille
- & Zhong Lin Wang
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Article
| Open AccessCrossover from gas-like to liquid-like molecular diffusion in a simple supercritical fluid
Within the phase diagram of pure substances, the supercritical state is not fully understood. Here the authors experimentally observe a gas-like to liquid-like crossover in the self-dynamics of supercritical fluid methane upon pressure increase.
- Umbertoluca Ranieri
- , Ferdinando Formisano
- & Livia E. Bove
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| Open AccessNeutron scattering and neural-network quantum molecular dynamics investigation of the vibrations of ammonia along the solid-to-liquid transition
Through neutron scattering experiments coupled with machine learning, the authors uncover the strong role of nuclear quantum effects in the dynamics of ammonia in both its solid and technologically relevant liquid phase.
- T. M. Linker
- , A. Krishnamoorthy
- & P. D. Vashishta
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Article
| Open AccessProbing the activated complex of the F + NH3 reaction via a dipole-bound state
Experimental characterization of the transition state in chemical reactions is challenging due to its transient nature. Here, Zhang et al. observe quantum states near the activated complex region of the F + NH3 → HF + NH2 reaction via a dipole-bound state of the FNH3- anion formed upon photodetachment, which allows probing regions of reactive potential energy surfaces out of the Franck-Condon-active areas.
- Rui Zhang
- , Shuaiting Yan
- & Chuangang Ning
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Article
| Open AccessThe role of memory-dependent friction and solvent viscosity in isomerization kinetics in viscogenic media
Molecular isomerization in solution is dependent on coupling of solute and solvent via memory-dependent friction. Here, by applying memory kernel extraction to molecular dynamics simulations, the authors demonstrate the role of friction in determining isomerization kinetics.
- Benjamin A. Dalton
- , Henrik Kiefer
- & Roland R. Netz
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Article
| Open AccessProgramming viscoelastic properties in a complexation gel composite by utilizing entropy-driven topologically frustrated dynamical state
Tuning the physical interactions and structures to govern the viscoelastic properties in hydrogels without altering the chemistry is challenging. Here the authors design a complexation gel composite and utilize the physical principle of topologically frustrated dynamical state to tune the correlated structures between the guest polycation chains and negatively charged host gels.
- Gui Kang Wang
- , Yi Ming Yang
- & Di Jia
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Article
| Open AccessScalable computation of anisotropic vibrations for large macromolecular assemblies
Normal mode analysis is a crucial step in structural biology, but is based on an expensive diagonalisation of the system’s Hessian. Here the authors present INCHING, a GPU-based approach to accelerate this task up to >250 times over current methods for macromolecular assemblies.
- Jordy Homing Lam
- , Aiichiro Nakano
- & Vsevolod Katritch
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| Open AccessOn the role of asymmetric molecular geometry in high-performance organic solar cells
The correlation between asymmetric molecular geometry of non-fullerene acceptors and their optoelectronic properties was unclear. Here, the authors found asymmetric ones exhibit increased open-circuit voltage compared to their symmetric counterparts due to reduced non-radiative charge recombination.
- Jinfeng Huang
- , Tianyi Chen
- & Lijian Zuo
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Article
| Open AccessQuantum phase synchronization via exciton-vibrational energy dissipation sustains long-lived coherence in photosynthetic antennas
Photosynthesis in biological systems occurs in a noisy environment that reduces the lifetime of coherences in the excitation energy transfer. Here the author demonstrate that long-lasting coherences are protected by quantum phase synchronization, realized in dimers by exciton-vibrational coupling where energy dissipation occurs predominantly in resonant anti-symmetric collective modes.
- Ruidan Zhu
- , Wenjun Li
- & Yuxiang Weng
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Article
| Open AccessSpiral packing and chiral selectivity in model membranes probed by phase-resolved sum-frequency generation microscopy
The properties of lipid membranes are intimately controlled by their complex heterogeneous structure. Here, the authors use phase-resolved sum-frequency generation microscopy to fully determine the hierarchical lipid packing from the molecular to the mesoscopic scale.
- Alexander P. Fellows
- , Ben John
- & Martin Thämer
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Article
| Open AccessThermodiffusive desalination
Current desalination technologies are energy intensive and suffer from membrane degradation and fouling. Here, authors propose and explore the potential of thermodiffusion as a means of membrane-free, single-phase thermal desalination. A pathway towards a feasible thermodiffusive desalination is provided.
- Shuqi Xu
- , Alice J. Hutchinson
- & Juan F. Torres
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Article
| Open AccessUniversal inter-molecular radical transfer reactions on metal surfaces
Radicals are expected to be inactive on metal surfaces. Here the authors describe general intermolecular radical transfer reactions on Ag and Cu surfaces and confirm the reaction mechanism by extensive control experiments.
- Junbo Wang
- , Kaifeng Niu
- & Lifeng Chi
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Article
| Open AccessAluminum corrosion–passivation regulation prolongs aqueous batteries life
Aqueous batteries have a short lifespan due to Al current collector corrosion and Li loss from side reactions on the anode. Here, the authors propose a prototype of self-prolonging aqueous Li-ion batteries by introducing hydrolyzation-type anodic additives to regulate Al corrosion-passivation.
- Binghang Liu
- , Tianshi Lv
- & Liumin Suo
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Article
| Open AccessUltrafast photoinduced C-H bond formation from two small inorganic molecules
The formation of C–H bonds via reaction of small inorganic molecules is of great interest for understanding the transition from inorganic to organic matter, but the detailed mechanisms remain elusive. Here, the authors demonstrate real-time visualization and coherent control of the ultrafast C–H bond formation dynamics in a light-induced bimolecular reaction from inorganic species.
- Zhejun Jiang
- , Hao Huang
- & Jian Wu
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| Open AccessDynamics of the charge transfer to solvent process in aqueous iodide
Solvated electrons can be formed through photo-induced charge-transfer-to-solvent electronic states of halide ions in water. Here, the authors use machine learning accelerated molecular dynamics simulations to follow the evolution of these states for aqueous iodide in detail.
- Jinggang Lan
- , Majed Chergui
- & Alfredo Pasquarello
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Article
| Open AccessSqueezing formaldehyde into C60 fullerene
The interconversion of the two spin isomers of formaldehyd has been studied in the gas phase but has never been observed experimentally in the condensed phase. Here the authors report the encapsulation of formaldehyde inside C60 cages and observe spin-isomer conversion of the formaldehyde guest molecules in the cryogenic solid state.
- Vijyesh K. Vyas
- , George R. Bacanu
- & Richard J. Whitby
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Article
| Open AccessControlled dissolution of a single ion from a salt interface
The strong ionic bond in salt is broken by electrostatic interactions with water, but direct observation at the level of a single ion is challenging. Here, the authors have visualized the preferential dissolution of an anion by manipulating a single water molecule.
- Huijun Han
- , Yunjae Park
- & Hyung-Joon Shin
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Article
| Open AccessUnderstanding of complex spin up-conversion processes in charge-transfer-type organic molecules
Kim et al. propose a model for the complex spin-flip process in charge-transfer-type thermally activated delayed fluorescence molecules, uncovering the origin of the high-lying triplet state, addressing a pressing issue discussed over the last decade.
- Hyung Suk Kim
- , Sang Hoon Lee
- & Chihaya Adachi
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Article
| Open AccessElectrostatic potentials of atomic nanostructures at metal surfaces quantified by scanning quantum dot microscopy
Surface averaging techniques offer only limited access to the electrostatic potentials of nanostructures, which are determined by shape, material, and environment. Here, the authors quantify these potentials for gold and silver adatom chains, explaining the mechanisms of dipole formation.
- Rustem Bolat
- , Jose M. Guevara
- & Christian Wagner
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Article
| Open AccessA programmable hybrid digital chemical information processor based on the Belousov-Zhabotinsky reaction
Computing platforms based on chemical processes can be an alternative to digital computers in some scenarios but have limited programmability. Here the authors demonstrate a hybrid computing platform combining digital electronics and an oscillatory chemical reaction and demonstrate its computational capabilities.
- Abhishek Sharma
- , Marcus Tze-Kiat Ng
- & Leroy Cronin
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Article
| Open AccessElectrofreezing of liquid water at ambient conditions
By performing long ab initio molecular dynamics simulations of water under external electric fields, for up to 500 picoseconds, the authors identify a transition to a ferroelectric amorphous phase at ambient conditions.
- Giuseppe Cassone
- & Fausto Martelli
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Article
| Open AccessUnified picture of vibrational relaxation of OH stretch at the air/water interface
Using femtosecond time-resolved heterodyne-detected vibrational sum-frequency generation spectroscopy the authors determine the vibrational relaxation (T1) time of the O-H stretch at the air/water interface by observing the decay of excited-state OH signals, providing a comprehensive picture of the interfacial vibrational relaxation process of water.
- Woongmo Sung
- , Ken-ichi Inoue
- & Tahei Tahara
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Article
| Open AccessThe role of interfacial donor–acceptor percolation in efficient and stable all-polymer solar cells
The underlying charge generation dynamics and structure-property relationships in organic solar cells are not fully understood. Here, the authors demonstrate that interfacial donor-acceptor percolation plays a key role in enabling both high charge generation efficiency and device stability.
- Zhen Wang
- , Yu Guo
- & Philip C. Y. Chow
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Article
| Open AccessMulticompartmental coacervate-based protocell by spontaneous droplet evaporation
Coacervate-based compartments are attractive as potential protocells, but formation and control of the compartments can be challenging. Here, the authors report the spontaneous formation of core-shell, cell-sized coacervate compartments driven by droplet evaporation.
- Cheng Qi
- , Xudong Ma
- & Zhou Liu
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| Open AccessImaging the state-to-state charge-transfer dynamics between the spin-orbit excited Ar+(2P1/2) ion and N2
The charge-transfer reaction Ar++N2 → Ar+N2+ has been largely studied as a model gas-phase reaction but many aspects remain to be understood. Here, differential cross sections of the reaction are measured and calculated with Ar+ prepared in 2P1/2 state, showing that the charge-transfer dynamics differs significantly for Ar+(2P1/2) compared to Ar+(2P3/2) when colliding with N2.
- Guodong Zhang
- , Dandan Lu
- & Hong Gao
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Article
| Open AccessObserving growth and interfacial dynamics of nanocrystalline ice in thin amorphous ice films
In-situ cryo-electron microscopy in thin amorphous ice films and ice-dynamics simulations reveal polymorph-dependent growth kinetics of nanoscale ice crystals. Hetero-crystalline ice exhibits anisotropic growth: fast-growing facets are associated with low-density interfaces, driving tetrahedral ordering of interfacial H2O molecules and accelerating ice growth.
- Minyoung Lee
- , Sang Yup Lee
- & Dong June Ahn
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Article
| Open AccessInvestigating the role of undercoordinated Pt sites at the surface of layered PtTe2 for methanol decomposition
Methanol on under-coordinated Pt sites at surface Te vacancies on layered PtTe2 decomposes at a probability >90 % which ultimately produces gaseous molecular hydrogen, methane, water and formaldehyde.
- Jing-Wen Hsueh
- , Lai-Hsiang Kuo
- & Meng-Fan Luo
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Article
| Open AccessMicroscopic mechanisms of pressure-induced amorphous-amorphous transitions and crystallisation in silicon
The mechanism of amorphous-amorphous transitions is highly debated. Here, the authors use molecular dynamics simulations to reveal transitions via nucleation-growth or spinodal decomposition, resembling a thermodynamic phase transition but influenced by mechanics.
- Zhao Fan
- & Hajime Tanaka
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Article
| Open AccessVibronic effects on the quantum tunnelling of magnetisation in Kramers single-molecule magnets
Quantum tunnelling of the magnetisation limits the performance of single-molecule magnets at low temperatures. Here, the authors combine ab initio and analytical methods to show that spin-phonon coupling subtly influences tunnelling via polaron formation.
- Andrea Mattioni
- , Jakob K. Staab
- & Nicholas F. Chilton
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| Open AccessHydrogen evolution with hot electrons on a plasmonic-molecular catalyst hybrid system
Direct participation of plasmon-induced hot electrons in the photoelectrocatalytic synthesis of hydrogen. This report solves a long-lasting contentious issue surrounding plasmonic materials on catalytic applications.
- Ananta Dey
- , Amal Mendalz
- & Jacinto Sá
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| Open AccessSpin relaxation of electron and hole polarons in ambipolar conjugated polymers
Spin and charge dynamics are inevitably linked, the study of the one often illuminating the other. Here, the authors study spin relaxation in ambipolar polymers and, backed by simulations, show how charge dynamics and wavefunction localization together set relaxation times up to room temperature.
- Remington L. Carey
- , Samuele Giannini
- & Henning Sirringhaus
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| Open AccessProbing the critical nucleus size in tetrahydrofuran clathrate hydrate formation using surface-anchored nanoparticles
The critical nucleus, which considered a key step in the formation of clathrate hydrates, has not yet been empirically confirmed. Here, the authors probe the critical nucleus size in clathrate formation of tetrahydrofuran and thus provide mechanistic insights.
- Han Xue
- , Linhai Li
- & Jianjun Wang
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Article
| Open AccessTowards a transferable fermionic neural wavefunction for molecules
Neural wavefunctions have become a highly accurate approach to solve the Schrödinger equation. Here, the authors propose an approach to optimize for a generalized wavefunction across compounds, which can help developing a foundation wavefunction model.
- Michael Scherbela
- , Leon Gerard
- & Philipp Grohs
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Article
| Open AccessColloidal pathways of amorphous calcium carbonate formation lead to distinct water environments and conductivity
The mechanism of calcium carbonate formation has been of interest for decades, but additive-controlled systems are poorly understood. Here the authors show that polycarboxylates facilitate bicarbonate entrapment and thereby inhibit nucleation. Distinct water environments in amorphous calcium carbonate nanoparticles arise from colloidal formation pathways and lead to mineral conductivity.
- Maxim B. Gindele
- , Sanjay Vinod-Kumar
- & Guinevere Mathies
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Article
| Open AccessInitial-site characterization of hydrogen migration following strong-field double-ionization of ethanol
Excitation of hydrogen-rich molecules often causes hydrogen migration, but characterisation of the individual sites is challenging. Here, the authors show that measurements of several isotopologues of ethanol can identify each hydrogen site’s contribution to the final products.
- Travis Severt
- , Eleanor Weckwerth
- & Itzik Ben-Itzhak
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Article
| Open AccessSpectroscopy and dynamics of the hydrated electron at the water/air interface
Hydrated electrons at the water/air interface participate in natural and synthetic processes, but investigation of their properties remains challenging. Here the authors show that most of their electron density is solvated below the dividing surface and solvates into the bulk in around 10 picoseconds, leaving its phenoxyl radical source at the interface.
- Caleb J. C. Jordan
- , Marc P. Coons
- & Jan R. R. Verlet
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Article
| Open AccessDirecting polymorph specific calcium carbonate formation with de novo protein templates
Most proteins mediating biomineralization in nature are not well structured, and the structures of the relevant protein-mineral interfaces regulating mineralization are elusive. Here, the authors computationally design proteins that modulate calcium carbonate mineralization to generate hybrid materials and elucidate the roles of designed proteins in controlling mineralization.
- Fatima A. Davila-Hernandez
- , Biao Jin
- & David Baker
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Article
| Open AccessSecond quantization of many-body dispersion interactions for chemical and biological systems
The many-body dispersion (MBD) framework models long-range electronic correlation and optical response of molecular systems. Here, the authors present a second-quantized MBD method that opens an efficient path to treating collective quantum fluctuations in molecular complexes with large number of atoms.
- Matteo Gori
- , Philip Kurian
- & Alexandre Tkatchenko
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Article
| Open AccessNonredox trivalent nickel catalyzing nucleophilic electrooxidation of organics
A good understanding of the mechanism behind organic electrooxidation is crucial for the development of efficient energy conversion technology. Here, the authors find that trivalent nickel is capable of oxidizing organics through a nucleophilic attack and electron transfer via a non-redox process.
- Yuandong Yan
- , Ruyi Wang
- & Zhigang Zou
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Article
| Open AccessThe role of halogens in Au–S bond cleavage for energy-differentiated catalysis at the single-bond limit
Investigation of the reaction process at the single-bond interface is key to understanding the catalytic reaction mechanism. Here, the authors develop a STM-BJ method to monitor the catalytic process from the perspective of single-bond energy.
- Peihui Li
- , Songjun Hou
- & Xuefeng Guo
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Article
| Open AccessThe unusual quadruple bonding of nitrogen in ThN
Nitrogen can form a maximum of three shared electron-pair bonds to complete its octet, suggesting the maximum bond order of nitrogen is three. Here, the authors report a joint photoelectron spectroscopy and quantum chemical study, showing a quadruple bond between nitrogen and thorium in thorium nitride.
- Zejie Fei
- , Jia-Qi Wang
- & Jun Li
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Article
| Open AccessMicroscopic theory, analysis, and interpretation of conductance histograms in molecular junctions
Conductance histograms are common setups to study molecular junctions, but the dispersion of the signals makes it difficult to interpret at microscopic level. Here the authors develop a physical model of molecular junctions that connects this observable with molecular properties.
- Leopoldo Mejía
- , Pilar Cossio
- & Ignacio Franco
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Article
| Open AccessStructural characterization of tin in toothpaste by dynamic nuclear polarization enhanced 119Sn solid-state NMR spectroscopy
Stannous fluoride (SnF2) is a common fluoride source and antimicrobial agent used in commercial toothpaste products. Here, the authors show how dynamic nuclear polarization can be used to perform 119Sn nuclear magnetic resonance spectroscopy experiments that probe the molecular structure of tin ions in commercial toothpastes.
- Rick W. Dorn
- , Scott L. Carnahan
- & Aaron J. Rossini
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| Open AccessDirect time-resolved observation of surface-bound carbon dioxide radical anions on metallic nanocatalysts
Understanding the activity and selectivity of metal catalysts requires elucidating the dynamics of CO2•− radicals bound to the surface. Here, the authors use pulse radiolysis to directly observe the stabilization process of CO2•− radicals at nanoscale metallic sites from nanoseconds to seconds.
- Zhiwen Jiang
- , Carine Clavaguéra
- & Mehran Mostafavi