Featured
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| 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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| 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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| 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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| 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
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Article
| Open AccessLanthanide-doped MoS2 with enhanced oxygen reduction activity and biperiodic chemical trends
Oxygen reduction reaction plays a key role in many applications of MoS2-based materials. Here, using first-principles simulations, the authors find the enhanced oxygen-reduction activity with a biperiodic chemical trend on the lanthanide-doped MoS2.
- Yu Hao
- , Liping Wang
- & Liang-Feng Huang
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Article
| Open AccessDirect observation of coherence transfer and rotational-to-vibrational energy exchange in optically centrifuged CO2 super-rotors
In this work the authors use coherent anti-Stokes Raman scattering to study collisional vibrational excitation in highly rotationally excited CO2 molecules prepared in an optical centrifuge.
- Timothy Y. Chen
- , Scott A. Steinmetz
- & Christopher J. Kliewer
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Article
| Open AccessEarly events in amyloid-β self-assembly probed by time-resolved solid state NMR and light scattering
Here the authors report time-resolved experiments showing that amyloid-β peptide molecules become partially structured even before they adhere to one another, within one millisecond. Peptide conformations change only slightly as assemblies grow in size for many minutes.
- Jaekyun Jeon
- , Wai-Ming Yau
- & Robert Tycko
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Article
| Open AccessNonthermal acceleration of protein hydration by sub-terahertz irradiation
The collective intermolecular dynamics of protein and water molecules, which overlap in subterahertz frequencies, are relevant for protein function expressions. Here the authors develop highly sensitive dielectric measurements, revealing that protein hydration is nonthermally accelerated by sub-terahertz irradiation.
- Jun-ichi Sugiyama
- , Yuji Tokunaga
- & Masahiko Imashimizu
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Article
| Open AccessProbing the atomically diffuse interfaces in Pd@Pt core-shell nanoparticles in three dimensions
Deciphering the structure and composition of bimetallic nanomaterial interfaces is key to understanding their properties. Here, the authors investigate the diffuse interfaces in Pd@Pt core-shell nanoparticles in 3D using electron tomography with atomic resolution.
- Zezhou Li
- , Zhiheng Xie
- & Jihan Zhou
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Article
| Open AccessUnidirectional rotation of micromotors on water powered by pH-controlled disassembly of chiral molecular crystals
‘Molecular motors, fuelled by various physical and chemical means, can perform asymmetric linear and rotary motions that are inherently related to their asymmetric shapes. Here, the authors describe silver-organic micro-complexes of random shapes that exhibit macroscopic unidirectional rotation on water surface through the asymmetric release of cinchonine or cinchonidine chiral molecules.
- Itai Carmeli
- , Celine M. Bounioux
- & Shachar E. Richter
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Article
| Open AccessRehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time
Electrocyclic reactions proceed through critical geometries, which are known as pericyclic transition states in thermal reactions and pericyclic minima in photochemical reactions. Here, the authors image the structure of a pericyclic minimum in real time using a combination of ultrafast electron diffraction and ab initio dynamics simulations.
- Y. Liu
- , D. M. Sanchez
- & T. J. A. Wolf
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Article
| Open AccessElectron diffraction of deeply supercooled water in no man’s land
Supercooled water in so-called “no man’s land” promises to reveal the origin of the water anomalies. Here, the authors use electron diffraction to provide the first characterization that spans this temperature range, which narrows down the array of possible explanations.
- Constantin R. Krüger
- , Nathan J. Mowry
- & Ulrich J. Lorenz
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Article
| Open AccessMeasurement-induced collective vibrational quantum coherence under spontaneous Raman scattering in a liquid
Spontaneous Raman scattering is classically understood as an incoherent process. Here, the authors demonstrate that macroscopic quantum coherence among billions of vibrating molecules in a liquid is generated when single photon detection and single spatio-temporal mode excitation are implemented.
- Valeria Vento
- , Santiago Tarrago Velez
- & Christophe Galland
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Article
| Open AccessFlattened 1D fragments of fullerene C60 that exhibit robustness toward multi-electron reduction
Fullerenes are compelling molecular materials, but the reason for their high robustness to multi-electron reduction is still debated. Here, the authors synthesize flattened 1D fragments of fullerene C60 with high robustness against multi-electron reduction.
- Masahiro Hayakawa
- , Naoyuki Sunayama
- & Aiko Fukazawa
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Article
| Open AccessComplex phase transitions and phase engineering in the aqueous solution of an isopolyoxometalate cluster
Complex phase transitions including gelation in dilute aqueous solutions of polyanionic clusters ([Mo7O24]6−) in the presence of (Fe(NO3)3) and attributed to the counterion association and overcharging on the clusters, have been identified.
- Zhi-Da Wang
- , Song Liang
- & Hong-Ying Zang
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Article
| Open AccessInelastic electron scattering induced quantum coherence in molecular dynamics
Photoabsorption and electron capture are known to induce quantum coherence in molecular dynamics. Here, the authors show that a non-resonant inelastic scattering of incoherent electrons induces such a coherence, which is the most general but hitherto unexplored way of triggering the coherent dynamics in a molecule.
- Akshay Kumar
- , Suvasis Swain
- & Vaibhav S. Prabhudesai
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Article
| Open AccessIn-plane and out-of-plane excitonic coupling in 2D molecular crystals
The mixing between Frenkel and charge-transfer characters in molecular excitons is difficult to analyze. Here, the authors demonstrate the onset and evolution of the mixing using 2D perylene molecular crystals by measuring the reorientation of emission transition dipoles with varying thicknesses.
- Dogyeong Kim
- , Sol Lee
- & Sunmin Ryu
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Article
| Open AccessQuantum dynamical effects of vibrational strong coupling in chemical reactivity
Experiments suggest that placing molecules in an infrared cavity alters their reactivity, an effect lacking a clear theoretical explanation. Here, the authors show that the key to understanding this process may lie in quantum light-matter interactions.
- Lachlan P. Lindoy
- , Arkajit Mandal
- & David R. Reichman
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Article
| Open AccessMany-body screening effects in liquid water
Electron screening is crucial to interpret inelastic X-ray scattering experiments in materials. Here the authors use a combined analysis based on the Bethe-Salpeter equation and time-dependent density functional theory to calculate the dielectric function and obtain the band gap of liquid water.
- Igor Reshetnyak
- , Arnaud Lorin
- & Alfredo Pasquarello
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Article
| Open AccessSingle-atomic-site platinum steers photogenerated charge carrier lifetime of hematite nanoflakes for photoelectrochemical water splitting
The achievable photocurrent of hematite, α-Fe2O3, is typically limited far below its theoretical limit. Here, the authors engineer single Pt atomic sites with surface oxygen vacancies into hematite photoanodes, which leads to enhanced photoelectrochemical water splitting.
- Rui-Ting Gao
- , Jiangwei Zhang
- & Limin Wu
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Article
| Open AccessFerricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy
Reliably identifying transient intermediates is crucial to elucidate chemical reaction mechanisms. Here, the authors use femtosecond Fe Kβ main line and valence-to-core x-ray emission spectroscopy to characterize a short-lived intermediate of the aqueous ferricyanide photo-aquation reaction.
- Marco Reinhard
- , Alessandro Gallo
- & Dimosthenis Sokaras
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Article
| Open AccessConfining donor conformation distributions for efficient thermally activated delayed fluorescence with fast spin-flipping
The distribution of dihedral angles in film state has significant influence on excited state lifetimes of thermally activated delayed fluorescence emitters. Here authors report conformation distribution confinement strategy to achieve fast spin-flipping for efficient organic light-emitting diodes.
- Weidong Qiu
- , Denghui Liu
- & Shi-Jian Su
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Article
| Open AccessDynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst
This work explores the concept of hemilability in single atom catalysts. The results imply that this effect can promote reactant activation and product desorption simultaneously to provide a potential approach to circumvent the Sabatier volcano.
- Zheng Chen
- , Zhangyun Liu
- & Xin Xu
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| Open AccessA molecular descriptor of intramolecular noncovalent interaction for regulating optoelectronic properties of organic semiconductors
Intramolecular noncovalent interactions can block molecules in a given conformation enhancing performance of organic semiconductors. Here, the authors report a molecular descriptor to weigh them that strongly correlates with the reorganization energy of excited or charged states.
- Meihui Liu
- , Xiao Han
- & Hui Huang
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Article
| Open AccessElectronic signatures of Lorentzian dynamics and charge fluctuations in lithiated graphite structures
Lithium graphite intercalation compounds are important for developing Li-ion batteries. Here authors simulate the interaction of high energy X-rays with Li ions intercalated in graphite and show that Li ions behave in an unexpected non-Gaussian fashion, leading to increasingly chaotic behaviour as the ion concentration reduces.
- Sasawat Jamnuch
- & Tod A. Pascal
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Article
| Open AccessSpectroscopic visualization and phase manipulation of chiral charge density waves in 1T-TaS2
Two-dimensional charge density waves in layered semiconductors may exhibit chirality. Here, the authors utilize thermal annealing to reversibly switch the in-plane chirality of charge density waves in 1T-TaS2 and demonstrate a vertical chirality-locking effect between the van der Waals-stacked layers.
- Yan Zhao
- , Zhengwei Nie
- & Jin Zhang
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Article
| Open AccessCondensation and asymmetric amplification of chirality in achiral molecules adsorbed on an achiral surface
The origin of homochirality in nature is an important but open question. Here, the authors provide insight into the physicochemical origin of homochirality through surface adsorption on the model of adlayers of achiral carbon monoxide molecules on an achiral Au(111) surface.
- Huiru Liu
- , Heping Li
- & Lan Chen
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Article
| Open AccessTwo-dimensional infrared-Raman spectroscopy as a probe of water’s tetrahedrality
Direct spectroscopic probes of the impact of structure on dynamical processes in liquids remain scarce. Here, the authors use molecular dynamics simulations to show that the correlation between vibrational coupling and the local tetrahedral structure of liquid water can be studied via hybrid terahertz- and infrared-Raman spectroscopy.
- Tomislav Begušić
- & Geoffrey A. Blake
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Article
| Open AccessAnomalous deep-red luminescence of perylene black analogues with strong π-π interactions
Perylene bisimide dyes are high-performance pigments that have red, maroon or black colors, but with typically only weak fluorescence in the solid state. Here, the authors report a series of π-stacked PBI derivatives that show highly efficient deep-red fluorescence in the solid state.
- Ningning Tang
- , Jiadong Zhou
- & Zengqi Xie
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Article
| Open AccessTowards the ground state of molecules via diffusion Monte Carlo on neural networks
An accurate ab initio calculation of molecules is fundamental to chemical and physical sciences. Here, the authors integrate a neural-network wavefunction into the fixed-node diffusion Monte Carlo, resulting in accurate calculations of a diverse range of systems, offering insights into complex many-body electronic wave functions.
- Weiluo Ren
- , Weizhong Fu
- & Ji Chen
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Article
| Open AccessNanoscale thermodynamics needs the concept of a disjoining chemical potential
Matter behaves differently at the nanoscale. Here, the author introduces the concept of a disjoining chemical potential for nanoscale thermodynamics, showing that thermodynamic functions depend on the environment, and suggests possible experimental verifications.
- W. Dong
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Article
| Open AccessHyperloop-like diffusion of long-chain molecules under confinement
Normally, the diffusion of the object is suppressed in the confined space. Here, by regulating the degrees of freedom of the molecule, authors demonstrate ultrafine diffusion in the sub-nano space.
- Jiamin Yuan
- , Mingbin Gao
- & Anmin Zheng
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Article
| Open AccessRapid handheld time-resolved circularly polarised luminescence photography camera for life and material sciences
Despite their high brightness and long-lived emission, lanthanide based circularly polarised luminophores have not been fully exploited for real-life application. Here, the authors present an all solid-state circularly polarised luminescence camera to facilitate ad hoc time-resolved enantioselective differential chiral contrast-based one-shot photography that can be applied in life and material sciences.
- Davide F. De Rosa
- , Patrycja Stachelek
- & Robert Pal
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Article
| Open AccessVisualizing defect dynamics by assembling the colloidal graphene lattice
Colloidal particles bonding via attractive patches mimic the bonding of atoms in atomic compounds and materials. By assembling patchy particles into the graphene lattice, the authors obtain insight into lattice defects in this important 2D material.
- Piet J. M. Swinkels
- , Zhe Gong
- & Peter Schall
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Article
| Open AccessObservation of Chiral-selective room-temperature phosphorescence enhancement via chirality-dependent energy transfer
Despite increasing interest in organic room temperature phosphorescence, it can still be challenging to determine mechanism and develop practical applications. Here, the authors report room temperature phosphorescent systems from chiral components, with strong phosphorescence observed only when both host and guest had the same chirality.
- Biao Chen
- , Wenhuan Huang
- & Guoqing Zhang
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Article
| Open AccessGas phase synthesis of the C40 nano bowl C40H10
Nanobowls represent building blocks of fullerenes and nanotubes as detected in combustion systems and deep space, but their formation mechanisms in these environments have remained elusive. Here, the authors explore the gas-phase formation of benzocorannulene and beyond to the C40 nanobowl.
- Lotefa B. Tuli
- , Shane J. Goettl
- & Ralf I. Kaiser