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Stability and Structure of the Aqueous LiTFSI-LiCl Interface Faraday Discuss. (IF 3.4) Pub Date : 2024-04-19 Hannah Wood, Hannah M Burnett, Robert Dryfe, Paola Carbone
It has recently been demonstrated that aqueous lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium chloride (LiCl) solutions can form stable liquid-liquid biphasic systems when both elec- trolyte phases have sufficiently high concentrations. In this work, we combine molecular dynamics simulations and experimental analysis to investigate what drives the formation of the interface and how
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Stabilization of lithium metal in concentrated electrolytes: effects of electrode potential and solid electrolyte interphase formation Faraday Discuss. (IF 3.4) Pub Date : 2024-04-16 Anusha Pradhan, Shoma Nishimura, Yasuyuki Kondo, Tomoaki Kaneko, Yu Katayama, Keitaro Sodeyama, Yuki Yamada
Lithium (Li) metal negative electrodes have enticed a wide attention for high-energy-density batteries. However, its low Coulombic efficiency (CE) due to parasitic electrolyte reduction has been an alarming concern. Concentrated electrolytes are one of the promising concepts that can stabilize the Li metal/electrolyte interface, thus increasing the CE; however, its mechanism has been still controversial
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Quantum Embedding for Molecules with Auxiliary Particles - The Ghost Gutzwiller Ansatz Faraday Discuss. (IF 3.4) Pub Date : 2024-04-16 Carlos Mejuto-Zaera
Strong/static electronic correlation mediates the emergence of remarkable phases of matter, and underlies the exceptional reactivity properties in transition metal-based catalysts. Modeling strongly correlated molecules and solids calls for multi-reference Ansätze, which explicitly capture the competition of energy scales characteristic of such systems. With the efficient computational screening of
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Towards Efficient Quantum Computing for Quantum Chemistry: Reducing Circuit Complexity with Transcorrelated and Adaptive Ansatz Techniques Faraday Discuss. (IF 3.4) Pub Date : 2024-04-16 Erika Magnusson, Aaron Fitzpatrick, Stefan Knecht, Martin Rahm, Werner Dobrautz
The near-term utility of quantum computers is hindered by hardware constraints in the form of noise. One path to achieving noise resilience in hybrid quantum algorithms is to decrease the required circuit depth -- the number of applied gates -- to solve a given problem. This work demonstrates how to reduce circuit depth by combining the transcorrelated (TC) approach with adaptive quantum ansätze and
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Mapping inorganic crystal chemical space Faraday Discuss. (IF 3.4) Pub Date : 2024-04-16 Hyunsoo Park, Anthony Onwuli, Keith Butler, Aron Walsh
The combination of elements from the Periodic Table defines a vast chemical space. Only a small fraction of these combinations yields materials that occur naturally or are accessible synthetically. Here, we enumerate binary, ternary, and quaternary element and species combinations to produce an extensive library of over 10^10 stoichiometric inorganic compositions. The unique combinations are vectorised
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Enhancement of essential cofactors for in vivo biocatalysis Faraday Discuss. (IF 3.4) Pub Date : 2024-04-16 Pattarawan Intasian, Chalermroj Sutthaphirom, Oliver Bodeit, Duangthip Trisrivirat, Ninlapan Kimprasoot, Juthamas Jaroensuk, Barbara Bakker, Edda Klipp, Pimchai Chaiyen
A scarcity of cofactors, necessary metabolites or substrates for in vivo enzymatic reactions are among the major barriers of product synthesis in metabolically engineered cells. This work compares our recently developed cofactor boosting strategy, which uses xylose reductase (XR) and lactose to increase the intracellular levels of reduced or oxidized nicotinamide adenine dinucleotide (phosphate) NAD(P)H
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What can Quantum Information Theory Offer to Quantum Chemistry? Faraday Discuss. (IF 3.4) Pub Date : 2024-04-12 Damiano Aliverti-Piuri, Kaustav Chatterjee, Lexin Ding, Ke Liao, Julia Liebert, Christian Schilling
It is the ultimate goal of this work to foster synergy between quantum chemistry and the flourishing field of quantum information theory. For this, we first translate quantum information concepts such as entanglement and correlation into the context of quantum chemical systems. In particular, we establish two conceptually distinct perspectives on correlation leading to a notion of orbital and particle
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Orbital optimisation in xTC transcorrelated methods Faraday Discuss. (IF 3.4) Pub Date : 2024-04-11 Daniel Kats, Evelin Martine Corvid Christlmaier, Thomas Schraivogel, Ali Alavi
We present a combination of the bi-orthogonal orbital optimisation framework with the recently introduced xTC version of transcorrelation. This allows us to implement non-iterative perturbation based methods on top of the transcorrelated Hamiltonian. Besides, the orbital optimisation influences results of other truncated methods, such as the distinguishable cluster with singles and doubles. The accuracy
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On the notion of strong correlation in electronic structure theory Faraday Discuss. (IF 3.4) Pub Date : 2024-04-10 Brad Ganoe, James Shee
Strong correlation has been said to have many faces, and appears to have many synonyms of questionable suitability. In this work we aim not to define the term once and for all, but to highlight one possibility that is both rigorously defined and physically transparent, and remains so in reference to molecules and quantum lattice models. We survey both molecular examples -- hydrogen systems (H$_\text{n}$
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Force and stress calculation with neural network wavefunction for solids Faraday Discuss. (IF 3.4) Pub Date : 2024-04-10 Yubing Qian, Xiang Li, Ji Chen
Accurate ab initio calculations of real solids are of fundamental importance in fields such as chemistry, phases and materials science. Recently, variational Monte Carlo (VMC) based on neural network wavefunction has been developed as a promising option to solve the existing challenges in ab initio calculations. In this study, we discuss the calculation of interatomic force and stress tensor of real
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Unravelling the complex speciation of halozincate ionic liquids using X-ray spectroscopies and calculations Faraday Discuss. (IF 3.4) Pub Date : 2024-04-09 Jake Seymour, Ekaterina Gousseva, Frances Towers Tompkins, Lewis Parker, Najaat Alblewi, Coby James Clarke, Shusaku Hayama, Robert Palgrave, Roger Bennett, Richard Paul Matthews, Kevin R. J. Lovelock
Using a combination of liquid-phase experimental X-ray spectroscopy experiments and small-scale calculations we have gained new insights into the speciation of halozincate anions in ionic liquids (ILs). Both core and valence X-ray photoelectron spectroscopy (XPS) were performed directly on the liquid-phase ILs, supplemented by Zn 1s X-ray absorption near edge structure (XANES) spectroscopy. Density
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Dispersions of magnetic nanoparticles in Water/ Ionic Liquid mixtures Faraday Discuss. (IF 3.4) Pub Date : 2024-04-09 Thiago Fiuza, Mitradeep Sarkar, Jesse Cornelius Riedl, Fabrice Cousin, Gilles Demouchy, Jerome Depeyrot, Emmanuelle Dubois, Regine Perzynski, Veronique Peyre
Nanoparticles (NPs) of iron oxide are dispersed in mixtures of water and ionic liquid, here ethylammonium nitrate (EAN) and the interactions NP/NP and NP/solvent are studied. They are analysed by Small Angle X-Ray Scattering and Dynamic Light Scattering coupled to Forced Rayleigh Scattering from 22° C to 80° C. The NPs are well dispersed as individual objects on the whole range of composition and temperature
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Transient IR Spectroscopy of Optically Centrifuged CO2 (R186−R282) and Collision Dynamics for the J=244−282 States Faraday Discuss. (IF 3.4) Pub Date : 2024-04-05 Michael E. Ritter, Simone Alexis DeSouza, Hannah Marie Ogden, Tara J Michael, Amy S Mullin
Collisions of optically centrifuged CO2 molecules with J=244-282 (Erot =22,800-30,300 cm-1) are investigated with high-resolution transient IR absorption spectroscopy to reveal collisional and orientational phenomena of molecules with hyper-thermal rotational energies. The optical centrifuge is a non-resonant optical excitation technique that uses ultrafast, 800 nm chirped pulses to drive molecules
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Chain-length dependent organisation in mixtures of hydrogenous and fluorous ionic liquids Faraday Discuss. (IF 3.4) Pub Date : 2024-04-05 Naomi Elstone, Emily Shaw, Karina Shimizu, Joshua Lai, Bruno Demé, Paul Lane, Matthew L Costen, Kenneth G McKendrick, Sarah Elizabeth Youngs, Sarah E. Rogers, Jose Nuno Canongia Lopes, Duncan W Bruce, John M. Slattery
As part of an ongoing study of the structure and properties of mixtures of ionic liquids in which one component has a hydrocarbon chain and the other a semiperfluorocarbon chain, we now report a study of the mixtures [C8MIM]1-x[C10MIM-F17]x[Tf2N], [C10MIM]1-x[C8MIM-F13]x[Tf2N] and [C10MIM]1-x[C10MIM-F17]x[Tf2N], where [C8MIM][Tf2N] is 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide, [C10MIM][Tf2N]
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Cumulant Green's function methods for molecules Faraday Discuss. (IF 3.4) Pub Date : 2024-04-04 Pierre-Francois Loos, Antoine Marie, Abdallah Ammar
The cumulant expansion of the Green’s function is a computationally efficient beyond-GW approach renowned for its significant enhancement of satellite features in materials. In contrast to the ubiquitous GW approximation of many-body perturbation theory, ab initio cumulant expansions performed on top of GW (GW+C) have demonstrated the capability to handle multi-particle processes by incorporating higher-order
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A Perspective on the Future of Quantum Chemical Software: The Example of the ORCA Program Package Faraday Discuss. (IF 3.4) Pub Date : 2024-04-04 Frank Neese
TBC
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Spinless formulation of linearized adiabatic connection approximation and its comparison with second order N-electron valence state perturbation theory Faraday Discuss. (IF 3.4) Pub Date : 2024-04-03 Yang Guo, Katarzyna Pernal
The adiabatic connection (AC) approximation, along with its linearized variant AC0, was introduced as a method of obtaining dynamic correlation energy. When using a complete active space self-consistent field (CASSCF) wave function as a reference, the AC0 approximation is considered one of the most efficient multi-reference perturbation theories. It only involves the use of 1$^{st}$- and 2$^{nd}$-order
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Accurate and Interpretable Representation of Correlated Electronic Structure via Tensor Product Selected CI Faraday Discuss. (IF 3.4) Pub Date : 2024-03-28 Nicole M Braunscheidel, Arnab Bachhar, Nicholas J. Mayhall
The task of computing wavefunctions that are accurate, yet simple enough mathematical objects to use for reasoning has long been a challenge in quantum chemistry. The difficulty in drawing physical conclusions from a wavefunction is often related to the generally large number of configurations with similar weights. In Tensor Product Selected CI, we use a locally correlated tensor product state basis
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Magnetic structure of a multiferroic compound: Cu2OCl2 Faraday Discuss. (IF 3.4) Pub Date : 2024-03-28 Julien Lévèque, Elisa Rebolini, Andrès Saùl, Marie-Bernadette Lepetit
The Cu2OCl2 compound has been shown to be a high-temperature spin-driven multiferroic system, with a linear magneto-electric coupling. In this paper we propose a complete study of its magnetic structure. We derive the low energy magnetic Hamiltonian using ab-initio multi-reference configuration interactions and the spin structure using Monte-Carlo simulations. Among the three magnetic structures proposed
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Gaussian Processes for Finite Size Extrapolation of Many-Body Simulations Faraday Discuss. (IF 3.4) Pub Date : 2024-03-25 Edgar Josue Landinez-Borda, Kenneth O. Berard, Annette Lopez, Brenda M Rubenstein
Key to being able to accurately model the properties of realistic materials is being able to predict their properties in the thermodynamic limit. Nevertheless, because most many-body electronic structure methods scale as a high-order polynomial, or even exponentially, with system size, directly simulating large systems in their thermodynamic limit rapidly becomes computationally intractable. As a result
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Linear ether-based highly concentrated electrolytes for Li-sulfur batteries Faraday Discuss. (IF 3.4) Pub Date : 2024-03-25 Toru Ishikawa, Shohei Haga, Keisuke Shigenobu, Taku Sudoh, Seiji Tsuzuki, Wataru Shinoda, Kaoru Dokko, Masayoshi Watanabe, Kazuhide Ueno
Li-S batteries have attracted attention as next-generation rechargeable batteries owing to their high theoretical capacity and cost-effectiveness. Sparingly solvating electrolytes hold promise because they suppress the dissolution and shuttling of polysulfide intermediates to increase the Coulombic efficiency and extend the cycle life. This study investigated the solubility of polysulfide (Li2S8) in
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Electric Field Induced Associations in the Double Layer of Salt-in-Ionic-Liquid Electrolytes Faraday Discuss. (IF 3.4) Pub Date : 2024-03-22 Daniel M. Markiewitz, Zachary Goodwin, Michael McEldrew, J. Pedro de Souza, Xuhui Zhang, Rosa Maria Espinosa-Marzal, Martin Z. Bazant
Ionic liquids (ILs) are an extremely exciting class of electrolytes for energy storage applications because of their unique combination of properties. Upon dissolving alkali metal salts, such as Li or Na based salts, with the same anion as the IL, an intrinsically asymmetric electrolyte can be created for use in batteries, known as a salt-in-ionic liquid (SiIL). These SiILs have been well studied in
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Wave mechanics in an ionic liquid mixture Faraday Discuss. (IF 3.4) Pub Date : 2024-03-22 Timothy Groves, Susan Perkin
Experimental measurements of interactions in ionic liquids and concentrated electrolytes over the past decade or so have revealed simultaneous monotonic and oscillatory decay modes. These observations have been hard to interpret using classical theories, which typically allow for just one electrostatic decay mode in electrolytes. Meanwhile, substantial progress in the theoretical description of dielectric
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Challenges with relativistic GW calculations in solids and molecules Faraday Discuss. (IF 3.4) Pub Date : 2024-03-20 Harsha Gaurav, Abraham Vibin, Dominika Zgid
For molecules and solids containing heavy elements, accurate electronic structure calculations require accounting not only for electronic correlations but also for relativistic effects. In molecules, relativity can lead to severe changes in the ground-state description. In solids, the interplay between both correlation and relativity can change the stability of phases or it can lead to an emergence
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Machine Learning-Driven Investigation of the Structure and Dynamics of the BMIM-BF₄ Room Temperature Ionic Liquid Faraday Discuss. (IF 3.4) Pub Date : 2024-03-19 Fabian Zills, Moritz René Schäfer, Samuel Tovey, Johannes Kästner, Christian Holm
Room-temperature ionic liquids are an exciting group of materials with the potential to revolutionize energy storage. Due to their chemical structure and means of interaction, they are challenging to study computationally. Classical descriptions of their inter- and intra-molecular interactions require time intensive parametrization of force-fields which is prone to assumptions. While ab initio molecular
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Cationic Micelles in Deep Eutectic Solvents: Effects of Solvent Composition Faraday Discuss. (IF 3.4) Pub Date : 2024-03-18 Iva Manasi, Stephen M King, Karen J Edler
Deep eutectic solvents (DES) are mixtures of hydrogen bond donors and acceptors that form strongly hydrogen-bonded room temperature liquids. Changing the H-bonding components and their ratios can alter the physicochemical properties of deep eutectic solvents (DES). Recent studies have shown p-toluene sulfonic acid (pTSA) forms room temperature liquids with choline chloride (ChCl) at different molar
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Harnessing Conformational Dynamics in Enzyme Catalysis to achieve Nature-like catalytic efficiencies: The Shortest Path Map tool for computational enzyme design Faraday Discuss. (IF 3.4) Pub Date : 2024-03-18 Cristina Duran, Guillem Casadevall, Sílvia Osuna
Enzymes exhibit diverse conformations, as represented in the so-called Free Energy Landscape (FEL). Such conformational diversity of enzymes provides them the ability to evolve towards novel functions. The challenge lies in identifying mutations that enhance specific conformational changes, especially if located in distal sites from the active site cavity. The Shortest Path Map (SPM) method, which
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Designing Michaelases: Exploration of novel protein scaffolds for iminium biocatalysis Faraday Discuss. (IF 3.4) Pub Date : 2024-03-18 Alejandro A. Gran-Scheuch, Stefanie Hanreich, Iris Keizer, Jaap Harteveld, Eelco Ruijter, Ivana Drienovska
Biocatalysis is becoming a powerful and sustainable alternative for asymmetric catalysis. However, enzymes are often restricted to metabolic and less complex reactivities. This can be addressed by protein engineering, such as incorporating new-to-nature functional groups into proteins through the so-called expansion of the genetic code to produce artificial enzymes. Selecting a suitable protein scaffold
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Computational study of the Mechanism of a polyurethane esterase A (PueA) from Pseudomonas chlororaphis Faraday Discuss. (IF 3.4) Pub Date : 2024-03-18 Katarzyna Świderek, Sergio Marti, Kemel Arafet, Vicent Moliner
The effective management of plastic waste has become a global imperative, given our reliance on a linear model in which plastics are manufactured, used once, and then discarded. This has led to the pervasive accumulation of plastic debris in landfills and environmental contamination. Recognizing this issue, numerous initiatives are underway to address the environmental repercussions associated with
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Deep Eutectic Solvents on a Tightrope: Balancing the Entropy and Enthalpy of Mixing Faraday Discuss. (IF 3.4) Pub Date : 2024-03-18 Adriaan van den Bruinhorst, Chiara Corsini, Guillaume Depraetère, Nithavong Cam, Agilio A.H. Padua, Margarida Costa Gomes
The large melting point depressions characterising deep eutectic solvents (DESs) are related to negative deviations from ideal mixing behaviour characterised by the excess Gibbs energy. Favourable excess Gibbs energies result from a balance between the excess entropy and enthalpy of mixing, which was experimentally determined for three choline chloride (ChCl) based mixtures using calorimetry. While
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Speciation of the proton in water-in-salt electrolytes Faraday Discuss. (IF 3.4) Pub Date : 2024-03-15 Kateryna Goloviznina, Alessandra Serva, Mathieu Salanne
Water-in-salt (WiS) electrolytes are promising systems for a variety of energy storage devices. Indeed, they represent a great alternative to conventional organic electrolytes thanks to their environmental friendliness, non-flammability, and good electrochemical stability. Understanding the behaviour of such systems and their local organisation is a key direction for their rational design and successful
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Overdetermination Method for Accurate Dynamic Ion Correlations in Highly Concentrated Electrolytes Faraday Discuss. (IF 3.4) Pub Date : 2024-03-14 Bernhard Roling, Tabita Pothmann, Maleen Middendorf, Monika Schönhoff, Christian Gerken, Pinchas Nürnberg
Highly concentrated battery electrolytes exhibit a low flammability as well as a high thermal and electrochemical stability, and they typically form stable solid electrolyte interphases in contact to electrode materials. The transport properties of these electrolytes in batteries are strongly influenced by correlated movements of the ions. In the case of a binary electrolyte, the transport properties
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Observation of cavitation dynamics in viscous deep eutectic solvents during power ultrasound sonication Faraday Discuss. (IF 3.4) Pub Date : 2024-03-14 Ben Jacobson, Shida Li, Paul Daly, Christopher E Elgar, Andrew Feeney, Paul Prentice, Andrew P Abbott
Deep Eutectic Solvents (DESs) are a class of ionic liquid with emerging applications in ionometallurgy. The characteristic high viscosity of DESs, however, limit mass transport and result in slow dissolution kinetics. Through targeted application of high-power ultrasound, ionometallurgical processing time can be significantly accelerated. This acceleration is primarily mediated by the cavitation generated
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Overcoming passivation through improved mass transport in dense ionic fluids Faraday Discuss. (IF 3.4) Pub Date : 2024-03-13 Evangelia Daskalopoulou, Philip Hunt, Christopher E Elgar, Minjun Yang, Andrew P Abbott, Jennifer Hartley
Deep Eutectic Solvents (DESs) have recently been shown to be part of a dense ionic fluid continuum between ionic liquids and concentrated aqueous brines. Charge transport was shown to be governed by fluidity, with no discontinuity between molar conductivity and fluidity irrespective of cation, charge density or ionic radius. By adjusting the activity of water and chloride ions, mass transport, speciation
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An Efficient Pyrrolysyl-tRNA Synthetase for Economical Production of MeHis-containing Enzymes Faraday Discuss. (IF 3.4) Pub Date : 2024-03-07 Amy Elizabeth Hutton, Jake Foster, James E. J. Sanders, Christopher J Taylor, Stefan A Hoffmann, Yizhi Cai, Sarah Louise Lovelock, Anthony Green
Genetic code expansion has emerged as a powerful tool in enzyme design and engineering, providing new insights into sophisticated catalytic mechanisms and enabling the development of enzymes with new catalytic functions. In this regard, the non-canonical histidine analogue Nδ-methylhistidine (MeHis) has proven especially versatile due to its ability to serve as a metal coordinating ligand or a catalytic
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Tuning peroxidase activity of artificial P450 peroxygenase by engineering redox-sensitive residues Faraday Discuss. (IF 3.4) Pub Date : 2024-03-07 Fengjie Jiang, Zihan Wang, Zhiqi Cong
Cytochrome P450 monooxygenases (P450s) are well recognized as versatile bio-oxidation catalysts. However, the catalytic functions of P450s are highly dependent on NAD(P)H and the redox partner proteins. Our group has recently reported to use a dual-functional small molecule (DFSM) for generating peroxygenase activity of P450BM3, a long-chain fatty acid hydroxylase from Bacillus megaterium. The DFSM-facilitated
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Identification of reaction intermediates in the decomposition of formic acid on Pd Faraday Discuss. (IF 3.4) Pub Date : 2024-03-07 Jan Fingerhut, Loïc Lecroart, Michael Schwarzer, Stefan Hörandl, Dmitriy Borodin, Alexander Kandratsenka, Alec M Wodtke, Daniel J Auerbach, Theofanis N. Kitsopoulos
Uncovering the role of reaction intermediates is crucial to developing an understanding of heterogeneous catalysis because catalytic reactions often involve complex networks of elementary steps. Unfortunately, the short lifetimes and low concentrations of intermediates present during reaction often makes observing and identifying them with surface sensitive spectroscopies experimentally challenging
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Adsorption and Vibrational Spectroscopy of CO on the Surface of MgO from Periodic Local Coupled-Cluster Theory Faraday Discuss. (IF 3.4) Pub Date : 2024-03-06 Hong-Zhou Ye, Timothy C. Berkelbach
The adsorption of CO on the surface of MgO has long been a model problem in surface chemistry. Here, we report periodic Gaussian-based calculations for this problem using second-order perturbation theory (MP2) and coupled-cluster theory with single and double excitations (CCSD) and perturbative triple excitations [CCSD(T)], with the latter two performed using a recently developed extension of the local
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Heterogeneous Li coordination in Solvent-in-Salt electrolytes enables high Li transference numbers Faraday Discuss. (IF 3.4) Pub Date : 2024-03-05 Anne Hockmann, Florian Ackermann, Diddo Diddens, Isidora Cekic-Laskovic, Monika Schönhoff
The transport properties and the underlying coordination structure of a ternary electrolyte consisting of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), 1,2-dimethoxyethane (DME), and 1,3-dioxolane (DOL) is studied over a wide concentration range up to a Solvent-in-Salt (SiS) electrolyte. Among other advantages for next-generation battery application, SiS electrolytes offer high lithium transference
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Degradation of PET microplastic particles to monomers in human serum by PETase Faraday Discuss. (IF 3.4) Pub Date : 2024-03-04 Ximena Lopez-Lorenzo, David Hueting, Eliott Bosshard, Per-Olof Syrén
More than 8 bton of plastic waste has been generated posing severe environmental consequences and health risks. Due to prolonged exposure, microplastic particles are found in human blood and other bodily fluids. Despite a lack of toxicity studies regarding microplastics, harmful effects for humans seem plausible and cannot be excluded. As small plastic particles readily translocate from the gut to
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Developing Deprotectase Biocatalysts for Synthesis. Faraday Discuss. (IF 3.4) Pub Date : 2024-03-01 Lisa Kennedy, Mariyah Sajjad, Michael Herrera, Peter Szieber, Natasza Rybacka, Yinan Zhao, Craig Steven, Zainab Alghamdi, Ivan Zlatkov, Julie Hagen, Chloe Lauder, Natalie Rudolfova, Magdalena Abramiuk, Karolina Bolimowska, Daniel Joynt, Angelica Lucero, Gustavo Perez Ortiz, Annamaria Lilienkampf, Alison N Hulme, Dominic James Campopiano
Organic synthesis often requires multiple steps where a functional group (FG) is concealed from reaction by a protecting group (PG). Common PGs include N-carbobenzyloxy (Cbz or Z) of amines and tert-butyloxycarbonyl (OtBu) of acids. An essential step is the removal of the PG, but this often requires excess reagents, extensive time and can have low % yield. An overarching goal of biocatalysis is to
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Friends and Relatives: Insight Into Conformational Regulation from Orthologues and Evolutionary Lineages using KIF and KIN Faraday Discuss. (IF 3.4) Pub Date : 2024-02-29 Dariia Yehorova, Rory M. Crean, Peter M Kasson, Shina Caroline Lynn Kamerlin
Noncovalent interaction networks provide a powerful means to represent and analyze protein structure. Such networks can represent both static structures and dynamic conformational ensembles. We have recently developed two tools for analyzing such interaction networks and generating hypotheses for protein engineering. Here, we apply these tools to the conformational regulation of substrate specificity
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Exploring the Selectivity of Cytochrome P450 for Enhanced Novel Anticancer Agent Synthesis Faraday Discuss. (IF 3.4) Pub Date : 2024-02-28 Janko Čivić, Neil Rory Mcfarlane, Joleen Masschelein, Jeremy Harvey
Cytochrome P450 monooxygenases are an extensive and unique class of enzymes, which can regio- and stereo-selectively functionalise hydrocarbons by way of oxidation reactions. These enzymes are naturally occurring but have also been extensively applied in a synthesis context, where they are used as efficient biocatalysts. Recently, a biosynthetic pathway where a cytochrome P450 monooxygenase catalyses
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Vibrational energy transfer in ammonia-helium collisions Faraday Discuss. (IF 3.4) Pub Date : 2024-02-28 Jérôme Loreau, Ad van der Avoird
While the rotational energy transfer of ammonia by rare gas atoms and hydrogen molecules has been the focus of many studies, little is known about its vibrational relaxation, even though transitions involving the umbrella bending mode have been observed in many astrophysical environments. Here we explore the vibrational relaxation of the umbrella mode of ammonia induced by collisions with helium atoms
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Oxygen-resistant [FeFe]hydrogenases: new biocatalysis tools for clean energy and cascade reactions Faraday Discuss. (IF 3.4) Pub Date : 2024-02-21 Francesca Valetti, Simone Morra, Lisa Barbieri, Sabrina Dezzani, Alessandro Ratto, Gianluca Catucci, Sheila J. Sadeghi, Gianfranco Gilardi
The use of enzymes to generate hydrogen, instead of using rare metal catalysts, is an exciting area of study in modern biochemistry and biotechnology, as well as biocatalysis driven by sustainable hydrogen. Thus far, the oxygen sensitivity of the fastest hydrogen-producing/exploiting enzymes, [FeFe]hydrogenases, has hindered their practical application, thereby restricting innovations mainly to their
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On-Surface Chemical Dynamics of Monolayer, Bilayer, and Many-Layered Graphene Surfaces Probed with Supersonic Beam Scattering and STM Imaging Faraday Discuss. (IF 3.4) Pub Date : 2024-02-21 Joshua Wagner, Ross Edel, Tim Grabnic, Bryan Wiggins, Steven J Sibener
We have developed the capability to elucidate interfacial reaction dynamics using an arguably unique combination of supersonic molecular beams combined with in situ STM visualization. These capabilities have been implemented in order to reveal the complex spatiotemporal correlations that govern the oxidation of graphitic systems spanning atomic-, nano-, and meso-length scales. In this study, the 3
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High-level analytical potential-energy-surface-based dynamics of the OH− + CH3CH2Cl SN2 and E2 reactions in full (24) dimensions Faraday Discuss. (IF 3.4) Pub Date : 2024-02-21 Andras B. Nacsa, Csenge Tokaji, Gabor Czako
We develop a coupled-cluster full-dimensional global potential energy surface (PES) for the OH− + CH3CH2Cl reactive system, using the ROBOSURFER program package, which automatically samples configurations along PES-based trajectories as well as performs ab initio computations with MOLPRO and fitting with the monomial symmetrization approach. The analytical PES accurately describes both the bimolecular
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Spiers Memorial Lecture: Challenges and prospects in organic photonics and electronics Faraday Discuss. (IF 3.4) Pub Date : 2024-02-21 Michele Catacchio, Mariapia Caputo, Lucia Sarcina, Cecilia Scandurra, Angelo Tricase, Verdiana Marchianò, Eleonora Macchia, Paolo Bollella, Luisa Torsi
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Towards Controlling Activity of a Peptide Asparaginyl Ligase (PAL) by Lumazine Synthetase Compartmentalization Faraday Discuss. (IF 3.4) Pub Date : 2024-02-20 TM Simon Tang, Louis YP Luk
Peptide asparaginyl ligases (PALs) hold significant potential in protein bioconjugation due to their excellent kinetic properties and broad substrate compatibility. However, realizing their full potential in biocatalytic applications requires precise control of their activity. Inspired by nature, we aimed to compartmentalize a representative PAL, OaAEP1-C247A, within protein containers to create artificial
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Determination of collision mechanisms at low energies using four-vector correlations Faraday Discuss. (IF 3.4) Pub Date : 2024-02-20 Pablo G Jambrina, James F. E. Croft, Balakrishnan Naduvalath, Hua Guo, F. Javier Aoiz
In molecular dynamics, a fundamental question is how the outcome of a collision depends on the relative orientation of the collision partners before their interaction begins (the stereodynamics of the process). The preference for a particular orientation of the reactant complex is intimately related to the idea of a collision mechanism and the possibility of control, as revealed in recent experiments
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Crossed molecular beam experiments and theoretical simulations on the multichannel reaction of toluene with atomic oxygen Faraday Discuss. (IF 3.4) Pub Date : 2024-02-20 Nadia Balucani, Gianmarco Vanuzzo, Pedro Recio, Adriana Caracciolo, Marzio Rosi, Carlo Cavallotti, Alberto Baggioli, Andrea Della Libera, Piergiorgio Casavecchia
Despite extensive experimental and theoretical studies on the kinetics of the O(3P) + C7H8 (toluene) reaction and a pioneering crossed molecular beam (CMB) investigation, the branching fractions (BFs) of the CH3C6H4O(methylphenoxy) + H, C6H5O(phenoxy) + CH3, and spin-forbidden C5H5CH3 (methylcyclopentadiene) + CO product channels remain an open question which has hampered the proper inclusion of this
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Reaction interferometry with ultracold molecules Faraday Discuss. (IF 3.4) Pub Date : 2024-02-16 Jeshurun Luke, Lingbang Zhu, Yi-Xiang Liu, Kang-Kuen Ni
We propose to coherently control the ultracold 2KRb $\rightarrow$ K$_2$ + Rb$_2$ reaction product state distribution via quantum interference. By leveraging that the nuclear spin degrees of freedom in the reaction maintain coherence, which was demonstrated in Liu and Zhu et al., arXiv:2310:07620, we explore the concept of a ``reaction interferometer.'' Such an interferometer involves splitting one
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Reaction Dynamics of the Methoxy Anion CH3O- with Methyl Iodide CH3I Faraday Discuss. (IF 3.4) Pub Date : 2024-02-16 Thomas Gstir, David Sundelin, Tim Michaelsen, Atilay Ayasli, Dasarath Swaraj, Jerin Judy, Fabio Zappa, Wolf Dietrich Geppert, Roland Wester
Studying larger nucleophiles in bimolecular nucleophilic substitution (SN 2) reactions bridges the gap from simple model systems to those relevant to organic chemistry. Therefore, we investigated the reaction dynamics between the methoxy anion (CH3O-) and iodomethane (CH3I) in our crossed-beam setup combined with velocity map imaging at the four collision energies 0.4, 0.7, 1.2, and 1.6 eV. We find
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Temperature dependent stereodynamics in surface scattering measured through subtle changes in the molecular wave function Faraday Discuss. (IF 3.4) Pub Date : 2024-02-14 Helen Chadwick, Gil Alexandrowicz
A magnetically manipulated molecular beam technique is used to change the rotational orientation of H2 molecules which collide with a stepped Cu(511) surface and explore how the polarisation dependence of molecules scattering into the specular channel changes as a function of surface temperature. At all temperatures, H2 molecules that are rotating like cartwheels are more likely to be scattered into
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On the Biocatalytic Synthesis of Silicone Polymers Faraday Discuss. (IF 3.4) Pub Date : 2024-02-13 Yuqing Lu, Lu Shin Wong
Polysiloxanes, with poly(dimethyl)siloxane (PDMS) being the most common example, are widely used in various industrial and applications due to their Si-O-Si backbone structure. The conventional synthesis of PDMS involves the hydrolysis of dichlorodimethylsilane, which raises environmental concerns due to the usage of chlorinated compounds. Herein, a biocatalytic approach for PDMS synthesis is demonstrated
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Reaction dynamics of S(3P) with 1,3-butadiene and isoprene: Crossed beam scattering, low temperature flow experiments, and high-level electronic structure calculations Faraday Discuss. (IF 3.4) Pub Date : 2024-02-07 Jinxin Lang, Casey D. Foley, Shameemah Thawoos, Abbas Behzadfar, Yanan Liu, Judit Zádor, Arthur Suits
Sulfur atoms serve as key players in diverse chemical processes from astrochemistry at very low temperature to combustion at high temperature. Building upon our prior findings showing cyclization to thiophenes following reaction of ground state sulfur atoms with dienes, we here extend this investigation to include many additional reaction products guided by detailed theoretical predictions. The outcomes
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Inelastic Scattering of NO(A2Σ+) + CO2; Rotation-Rotation Pair-Correlated Differential Cross Sections Faraday Discuss. (IF 3.4) Pub Date : 2024-02-06 Joseph G Leng, Thomas R Sharples, Martin Fournier, Kenneth G McKendrick, Luca Craciunescu, Martin J. Paterson, Matthew L Costen
A crossed beam velocity-map ion-imaging appratus has been used to determine differential cross sections (DCSs) for rotationally inelastic scattering of NO(A2Σ+, v = 0, j = 0.5) with CO2, as a function of both NO(A, v = 0, N′) final state and the coincident final rotational energy of the CO2. The DCSs are dominated by forward-peaked scattering for all N′, with significant rotational excitation of CO2
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Application of rational enzyme engineering in a new route to Etonogestrel and Levonorgestrel: Carbonyl reductase bioreduction of ethyl secodione Faraday Discuss. (IF 3.4) Pub Date : 2024-02-06 Daniel F.A.R. Dourado, Andrew Rowan, Sergej Maciuk, Jenny Spratt, Gareth Brown, Gray Darren, Jill Caswell, Alexandra Carvalho, Fernando Turespinosa, Drazen Pavlovic, Derek Quinn, Tom Moody, Stefan Mix
Women in developing countries still face enormous challenges when accessing reproductive health care. Access to voluntary family planning empowers women allowing them to complete their education and join the paid workforce. This effectively helps to end poverty, hunger and promotes good health for all. According to the United Nations (UN) organization, in 2022, an estimated 257 million women still
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Probing the Interfacial Structure of Aqueous Surfactants through Helium Atom Evaporation Faraday Discuss. (IF 3.4) Pub Date : 2024-02-05 Xiao-Fei Gao, David J. Hood, Timothy H. Bertram, Gilbert M. Nathanson
Dissolved helium atoms evaporate from liquids in super-Maxwellian speed distributions because their interactions are too weak to enforce full thermal equilibration at the surface as they are "squeezed" out of solution. The excess speeds of these He atoms reflect their final interactions with solvent and solute molecules at the surfaces of water and other liquids. We extend this observation by monitoring
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Scattering resonances in the rotational excitation of HDO by Ne and normal-H2: theory and experiment Faraday Discuss. (IF 3.4) Pub Date : 2024-02-01 Ricardo Manuel García-Vázquez, Astrid Bergeat, Otoniel Denis-Alpizar, Alexandre Faure, Thierry Stoecklin, sebastien morales
The rotational excitation of singly deuterated water molecule (HDO) by a heavy atom (Ne) and a light diatomic molecule (H2) is investigated theoretically and experimentally in the near-threshold regime. Crossed-molecular beam measurements with a variable crossing angle are compared to close-coupling calculations based on high-accuracy potential energy surfaces. The two lowest rotational transitions