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| 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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Article
| Open AccessGeneralised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks
The kinetics of guest-induced structural transition shown by flexible metal–organic frameworks (MOFs) remain poorly understood despite being crucial for process design. Here, three MOFs are studied to reveal the framework-dependent kinetic nature.
- Yuta Sakanaka
- , Shotaro Hiraide
- & Satoshi Watanabe
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Article
| 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
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Article
| Open AccessRevealing the role of double-layer microenvironments in pH-dependent oxygen reduction activity over metal-nitrogen-carbon catalysts
By combining theoretical simulations and spectroscopic measurements, Peng Li et al. demonstrated that distinct interfacial double-layer structures play a key role in the pH-dependent oxygen reduction kinetics over metal-nitrogen-carbon catalysts.
- Peng Li
- , Yuzhou Jiao
- & Shengli Chen
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Article
| Open AccessRedox signaling-driven modulation of microbial biosynthesis and biocatalysis
Microbial communication has significant implications for industrial applications, but constructing communication systems which support coordinated behaviors is challenging. Here, the authors report an electron transfer triggered redox communication network and demonstrate its ability to coordinate microbial metabolism.
- Na Chen
- , Na Du
- & Quan Yuan
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Article
| Open AccessDefying decomposition: the curious case of choline chloride
A rational design of deep eutectic solvents (DESs) is hindered because fundamental DES components, such as choline chloride (ChCl), decompose before melting. Here authors determine the melting properties of ChCl, unveiling ionic plastic crystals as a platform for DESs that meet modern sustainability, health, and safety requirements.
- Adriaan van den Bruinhorst
- , Jocasta Avila
- & Margarida Costa Gomes
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Article
| Open AccessKinetics of the xanthophyll cycle and its role in photoprotective memory and response
This study explores how the photosynthetic alga Nannochloropsis oceanica, rapidly adapts to changing light conditions, using a short-term “memory" system involving the xanthophyll cycle, which is widespread in photosynthetic organisms.
- Audrey Short
- , Thomas P. Fay
- & Graham R. Fleming
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Article
| Open AccessLiquid spherical shells are a non-equilibrium steady state of active droplets
Dissipative structures are governed by non-equilibrium thermodynamics. Here, the authors describe a size-dependent transition from active droplets to active spherical shells—a dissipative structure that arises from reaction diffusion gradients.
- Alexander M. Bergmann
- , Jonathan Bauermann
- & Job Boekhoven
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Article
| Open AccessIntegrative solution structure of PTBP1-IRES complex reveals strong compaction and ordering with residual conformational flexibility
An integrated structural biology approach is utilized to elucidate the solution structure of the polypyrimidine-tract binding protein 1 (PTBP1/hnRNP I) complexed with an internal ribosome entry site (IRES) RNA fragment from encephalomyocarditis virus (EMCV).
- Georg Dorn
- , Christoph Gmeiner
- & Frédéric H.-T. Allain
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Article
| Open AccessTunable encapsulation of sessile droplets with solid and liquid shells
Encapsulated liquids are important for several microreactor applications, including (bio)chemistry in confined spaces. Here, the authors report on oil-infused particle shells that allow control of shell thickness, stability, and permeability for applications in crystal growth and cell cultivation.
- Rutvik Lathia
- , Satchit Nagpal
- & Prosenjit Sen
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Article
| Open AccessUniversal machine learning for the response of atomistic systems to external fields
External fields, despite their significant influence on chemical processes, have been largely ignored in current machine learning potentials. Here, the authors introduce a field-induced model that captures system-field interactions rigorously.
- Yaolong Zhang
- & Bin Jiang
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Article
| Open AccessLight-driven nucleation, growth, and patterning of biorelevant crystals using resonant near-infrared laser heating
Natural biominerals deposit with precise spatial and temporal control, but such control is difficult to replicate artificially. Here, the authors start, steer, and stop the crystallization of biorelevant minerals by user-defined light patterns.
- Marloes H. Bistervels
- , Balázs Antalicz
- & Willem L. Noorduin
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Article
| Open AccessInduced photoelectron circular dichroism onto an achiral chromophore
An achiral molecule can acquire a chiral spectroscopic signature when interacting with a chiral host. Here, the authors report the asymmetry in the electron distribution following ionisation of phenol complexed by chiral methyloxirane, which reflects an induced chirality onto the achiral phenol.
- Etienne Rouquet
- , Madhusree Roy Chowdhury
- & Anne Zehnacker
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Article
| Open AccessStructure determination of ζ-N2 from single-crystal X-ray diffraction and theoretical suggestion for the formation of amorphous nitrogen
The ζ-N2 phase is key for comprehending the pressure-driven molecular to polymeric shift in nitrogen. Here, the authors resolved the crystal structure of ζ-N2 and identified a gradual delocalization of its electronic density under pressure, culminating in the initiation of nitrogen’s polymerization.
- Dominique Laniel
- , Florian Trybel
- & Natalia Dubrovinskaia
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Article
| Open AccessPromoting multiexciton interactions in singlet fission and triplet fusion upconversion dendrimers
The impact of multiexcitonic through-space interactions in macromolecular architectures is poorly investigated. Here the authors use dendritic macromolecules to study the effect of interchromophore interactions on the dynamics of multiexciton generation and decay as a function of dendrimer generation.
- Guiying He
- , Emily M. Churchill
- & Luis M. Campos
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Article
| Open AccessStrong structuring arising from weak cooperative O-H···π and C-H···O hydrogen bonding in benzene-methanol solution
Understanding liquid behavior is a challenge due to their disorder nature and rapid molecular rearrangements. Here, the authors show how weak interactions between OH groups and aromatic rings can participate in cooperative mechanisms that give rise to highly structured molecular arrangements in the liquid state.
- Camilla Di Mino
- , Andrew G. Seel
- & Neal T. Skipper
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Article
| Open AccessOrganic radical ferroelectric crystals with martensitic phase transition
Organic martensitic compounds are emerging smart materials with intriguing physical properties. Here authors show that upon H/F substitution a series of 1,4,5,8-naphthalenediimide derivatives exhibit reversible ferroelectric and martensitic transitions with a large thermal hysteresis.
- Nan Zhang
- , Wencong Sun
- & Han-Yue Zhang
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Article
| Open AccessIdentification of a common ice nucleus on hydrophilic and hydrophobic close-packed metal surfaces
One key challenge in water science is to create a universal model that can predict the arrangement of water/solid interfaces. Here, the authors use STM and noncontact-AFM to discover common water clusters during the initial growth on hydrophilic and hydrophobic close-packed metal surfaces.
- Pengcheng Chen
- , Qiuhao Xu
- & Nan Yao
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Article
| Open AccessDirectly imaging excited state-resolved transient structures of water induced by valence and inner-shell ionisation
Capturing the detailed structural evolution of electronic excited states is a challenging but critical step to understand and control ultrafast molecular dynamics. Here, combining a Coulomb explosion imaging approach and molecular dynamics simulations, the authors retrieve the transient geometry of the ground and excited states of D2O mono- and dication with few femtosecond, few picometre accuracy.
- Zhenzhen Wang
- , Xiaoqing Hu
- & Dajun Ding
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Article
| Open AccessEarly-stage bifurcation of crystallization in a sphere
Thermodynamics predicts equilibrium crystal structures and kinetics discover the pathway to form them. The authors investigate the interplay of thermodynamics and kinetics in the formation of colloidal clusters and reveal a bifurcation at an early stage of the crystallization process.
- Chrameh Fru Mbah
- , Junwei Wang
- & Michael Engel
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Article
| Open AccessDrug classification with a spectral barcode obtained with a smartphone Raman spectrometer
Smartphones are ubiquitous devices that have permeated into our daily life. Here, the authors demonstrate that a Smartphone Raman spectrometer can be used for drug classification by using a convolutional neural network to process its spectral barcode.
- Un Jeong Kim
- , Suyeon Lee
- & Hyuck Choo
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Article
| Open AccessSynthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[a,i]fluorenylidene) and its derivatives
The rotation of a carbon double bond in an alkene can be efficiently accelerated by creating the high strain ground state and stabilizing the transition state of the process. Here, the authors report the synthesis, structures, and properties of several highly twisted alkenes.
- Hao-Wen Kang
- , Yu-Chiao Liu
- & Yao-Ting Wu
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Article
| Open AccessRoom temperature valley polarization via spin selective charge transfer
Valleytronics is a portmanteau of ‘valley’ and ‘electronics’ and refers to the use of the valley degree of freedom, present in some materials, for encoding and processing information. Here, Shrestha et al demonstrate a room temperature valley polarization in heterostructures composed of molybdenum disulfide and a chiral lead halide perovskite, an important step in development of valleytronics.
- Shreetu Shrestha
- , Mingxing Li
- & Mircea Cotlet
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Article
| Open AccessAtomic-level structure determination of amorphous molecular solids by NMR
The atomic-level ensemble structure of an amorphous form of a drug is determined by combining NMR experiments with molecular dynamics simulations and machine-learned chemical shifts. The structure explains the stabilization of the amorphous form.
- Manuel Cordova
- , Pinelopi Moutzouri
- & Lyndon Emsley
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Article
| Open AccessAllosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis
The mechanisms by which changes in local geometries of receptor sites lower activation reaction barriers in electronically uncoupled, remote reaction moieties remain relatively unexplored. Here, the authors demonstrate allosteric acceleration in the thermal isomerization of an alkene triggered by the binding of a metal ion to a remote receptor site.
- Yichen Yu
- , Robert T. O’Neill
- & Stephen L. Craig
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Article
| Open AccessMinimizing non-radiative decay in molecular aggregates through control of excitonic coupling
Exciton delocalization in molecular aggregates is suggested to counteract the Energy Gap Law. Here, authors reveal the underlying physical picture and find the optimal excitonic coupling that minimizes nonradiative decay by nearly exact simulations.
- Yuanheng Wang
- , Jiajun Ren
- & Zhigang Shuai
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Article
| Open AccessMolecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics
The oxidation of aromatics contributes significantly to the formation of atmospheric aerosol. Using toluene as an example the authors demonstrate a molecular rearrangement channel in the oxidation mechanism and show that the bicyclic peroxy radicals are much less stable than previously thought and can lead to aerosol-forming low-volatility products with up to 9 oxygen atoms on sub-second timescales
- Siddharth Iyer
- , Avinash Kumar
- & Matti Rissanen
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Article
| Open AccessVisualization of π-hole in molecules by means of Kelvin probe force microscopy
A π-electron-deficient cavity in halogen-substituted polyaromatic hydrocarbon compounds, the so-called π-holes, have been predicted theoretically. Here authors present an experimental resolution of the πhole on a single molecule using the Kelvin probe force microscopy.
- B. Mallada
- , M. Ondráček
- & P. Jelínek
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Article
| Open AccessTheory predicts UV/vis-to-IR photonic down conversion mediated by excited state vibrational polaritons
Vibrational polaritons steer chemical reactions and control quantum states for information processing. Here the authors predict their formation during electronic photo-excitation, enabling a down-conversion of visible to infrared photons.
- Connor K. Terry Weatherly
- , Justin Provazza
- & Roel Tempelaar
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Article
| Open AccessEnantioselectivity of discretized helical supramolecule consisting of achiral cobalt phthalocyanines via chiral-induced spin selectivity effect
Experimental realizations of absolute enantioselection, without chiral catalysis or chiral ingredients, has been challenging. Here, the authors obtain enantioselectivity in mesoscale helical supramolecules consisting only of achiral molecules by exploiting chiral-induced spin selectivity (CISS) effect.
- Hiroki Aizawa
- , Takuro Sato
- & Hiroshi M. Yamamoto
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Article
| Open AccessChirality control of a single carbene molecule by tip-induced van der Waals interactions
The control of molecular chirality is of great interest in stereochemistry and biochemistry. Here, the authors show how to alter the chirality dynamics of a single molecule through tip-induced van der Waals interactions.
- Yunjun Cao
- , Joel Mieres-Perez
- & Karina Morgenstern
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Article
| Open AccessConfining charge-transfer complex in a metal-organic framework for photocatalytic CO2 reduction in water
Maji and coworkers report the selective conversion of CO2 to CH4 under visible light by utilizing a charge transfer complex within Zr-MOF-808 pores. The complex ultimately facilitates efficient multielectron reduction at the Zr-catalytic center.
- Sanchita Karmakar
- , Soumitra Barman
- & Tapas Kumar Maji
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Article
| Open AccessEnhancing reactivity of SiO+ ions by controlled excitation to extreme rotational states
Control of chemical reactivity through excitation of rotational states is a relatively unexplored process that may play a role in interstellar chemistry. Here the authors show a marked acceleration of the hydrogen abstraction reaction between SiO+ and H2 by exciting super-rotor states of SiO+, in a joint experimental and theoretical study.
- Sruthi Venkataramanababu
- , Anyang Li
- & Brian C. Odom
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Article
| Open AccessAttosecond delays between dissociative and non-dissociative ionization of polyatomic molecules
The role of nuclear motion on photoionization delays is an interesting open question. Here the authors study photoionization delays in dissociative and non-dissociative ionization of a polyatomic molecule and explore the effect of isotopic substitution.
- Xiaochun Gong
- , Étienne Plésiat
- & Hans Jakob Wörner
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Article
| Open AccessSHARPER-DOSY: Sensitivity enhanced diffusion-ordered NMR spectroscopy
Since its discovery, the sensitivity of Nuclear Magnetic Resonance has increased steadily. Here the authors report on a liquid-state NMR methodology that increases the sensitivity of the diffusion coefficient measurements 10–100- fold, allowing to use microgram quantities of compounds, while reducing the measurement time to few minutes.
- George Peat
- , Patrick J. Boaler
- & Dušan Uhrín
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Article
| Open AccessMesitylated trityl radicals, a platform for doublet emission: symmetry breaking, charge-transfer states and conjugated polymers
Neutral π-radicals are potential emitters for optoelectronic devices due to the absence of energetically low-lying non-emissive states. Here, the authors report mesityl-substituted tris(2,4,6-trichlorophenyl)methyl radicals and achieve maximum device efficiency of 28% at a wavelength of 689 nm.
- Petri Murto
- , Rituparno Chowdhury
- & Hugo Bronstein
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Article
| Open AccessHydrodynamic spin-orbit coupling in asynchronous optically driven micro-rotors
Hydrodynamically coupled rotors can be used to describe interactions ranging from molecular machines to atmospheric dynamics. Modin et al. show that optically-driven rotors in a non-tweezing beam can freely diffuse while spinning asynchronously and develop an analytical hydrodynamic model to explain.
- Alvin Modin
- , Matan Yah Ben Zion
- & Paul M. Chaikin
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Article
| Open AccessOxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors
In this study, the authors correlate the kinetics of lateral photooxidation in WS2 and MoS2 monolayers with their crystallographic defects and environmental parameters, showing a charge transfer mechanism that does not follow the Marcus-Gerischer charge transfer theory.
- Ning Xu
- , Li Shi
- & Songlin Li
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Article
| Open AccessLongevity gene responsible for robust blue organic materials employing thermally activated delayed fluorescence
High throughput virtual screening of robust blue thermally activated delayed fluorescent emitters has yet been implemented. Here, authors reveal a linear relationship of the difference between bond dissociate energy and first triplet state energy with the logarithm of device operational lifetime.
- Qing-Yu Meng
- , Rui Wang
- & Juan Qiao
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Article
| Open AccessFundamental investigations on the ionic transport and thermodynamic properties of non-aqueous potassium-ion electrolytes
K-ion batteries may have rate advantages over Li-ion batteries due to the larger size of the cation. Here, the authors characterize the ionic transport and thermodynamic properties of non-aqueous K-ion electrolyte solutions demonstrating higher K-ion mobility than the Li-ion counterpart.
- Shobhan Dhir
- , Ben Jagger
- & Mauro Pasta
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Article
| Open AccessRegulating the proximity effect of heterocycle-containing AIEgens
Proximity effect (PE) can impact the behaviour of heterocyclic luminogens, but is rarely used to manipulate the aggregation-induced emission (AIE) related properties. Here, the authors systematically illustrate the impacts of PE and AIE on luminescent behaviors.
- Jianyu Zhang
- , Yujie Tu
- & Ben Zhong Tang
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Article
| Open AccessAltering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4′−bipyridine
Despite the distinct electronic properties of the wide variety Cm3+ compounds that have been prepared to date, no singlecrystal structural characterization of a complex containing a Cm−C bond has been reported. Here the authors report the synthesis of a Cm complex bearing trimethylsilylcyclopentadienyl and 4,4’-bipyridine ligands with a low energy emission and identify the 4,4’-bipyridine ligand as the primary quenching agent.
- Brian N. Long
- , María J. Beltrán-Leíva
- & Thomas E. Albrecht-Schönzart
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Article
| Open AccessManipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling
Mechanistic understanding of how light-matter interaction alters chemical reactivities remains a challenge. Here, the authors show both hydrogen bond dissociation rate and pathways can be modified through cavity-modified molecular coupling patterns.
- Qi Yu
- & Joel M. Bowman
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Article
| Open AccessMelting domain size and recrystallization dynamics of ice revealed by time-resolved x-ray scattering
The phase transition between water and ice is a ubiquitous phenomenon in nature. Here, the authors conduct a time-resolved x-ray scattering experiment using X-ray Free Electron Lasers to elucidate a comprehensive picture of the melting and recrystallization dynamics of crystalline ice, based on direct structural information.
- Cheolhee Yang
- , Marjorie Ladd-Parada
- & Kyung Hwan Kim
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Article
| Open AccessRevealing core-valence interactions in solution with femtosecond X-ray pump X-ray probe spectroscopy
Pump-probe spectroscopy is routinely used to interrogate ultrafast valence electronic and vibrational dynamics in complex systems. Here, the authors extend this technique to the X-ray regime using a sequence of femtosecond X-ray pulses to understand core-valence interactions in a solvated molecular complex.
- Robert B. Weakly
- , Chelsea E. Liekhus-Schmaltz
- & Munira Khalil
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Article
| Open AccessLocal cation-tuned reversible single-molecule switch in electric double layer
A common approach to design single-molecule switch is to use molecular backbones in response to external stimulus, but often requires complex organic synthesis. Here, Tong et al. show how to in situ control of the molecule-electrode contact using electrochemical gating to realize a reversible switch.
- Ling Tong
- , Zhou Yu
- & Xiao-Shun Zhou
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Article
| Open AccessRealistic phase diagram of water from “first principles” data-driven quantum simulations
The molecular modelling of water has been a long sought-after goal in computational sciences for more than 50 years. Here, the authors show that the data-driven many-body MB-pol potential can provide a realistic representation of the phase diagram of water.
- Sigbjørn Løland Bore
- & Francesco Paesani
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Article
| Open AccessCoherent Stokes Raman scattering microscopy (CSRS)
Coherent Stokes Raman scattering (CSRS) has never been explored previously for chemical imaging due to a strong fluorescence background. Here, the authors demonstrate the first fluorescence-free CSRS laser scanning microscope and predict CSRS’ unique backscattering properties.
- Sandro Heuke
- & Hervé Rigneault
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Article
| Open AccessRevealing CO2 dissociation pathways at vicinal copper (997) interfaces
Catalytic CO2 dissociation pathways are selectively determined by surface geometry in heterogeneous catalysis. The authors find that the stepped Cu surfaces effectively affect CO2 activation in elementary reaction steps at the atomic level
- Jeongjin Kim
- , Youngseok Yu
- & Jeong Young Park