Faraday Discussions最新文献

{"title":"Tailored Carbon Dioxide Capacity in Carboxylate-Based Ionic Liquids†","authors":"Nicolas Scaglione, Jocasta Avila, Agilio A.H. Padua, Margarida Costa Gomes","doi":"10.1039/d4fd00052h","DOIUrl":"https://doi.org/10.1039/d4fd00052h","url":null,"abstract":"We used a library of thermally stable tetraalkylphosphonium carboxylate ILs that were easily pre- pared from available carboxylic acids. Depending on the 𝑝𝐾𝑎 of the precursor acids, the resulting ionic liquids either dissolve or reversibly chemically absorb CO2, with some exhibiting notable gas capacities, reaching up to 0.2 mole fraction of CO2 at 1 bar and 343 K. While equilibrium con- stants and ionic liquid capacities generally correlate with the 𝑝𝐾𝑎 of the acids, certain exceptions underscore the influence of liquid structure and physical properties, elucidated through molecular dynamics simulations and density functional theory (DFT) calculations. Unlike trends observed in other CO2-absorbing ILs, phosphonium carboxylates do not experience increased viscosity upon CO2 absorption; instead, enhanced diffusivities are observed, facilitating efficient gas-liquid trans- fer and reducing energy requirements in carbon capture processes.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140797730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Permutation Symmetry in Spin Adapted Many-Body Wave Functions","authors":"Maru Song, Ali Alavi, Giovanni Li Manni","doi":"10.1039/d4fd00061g","DOIUrl":"https://doi.org/10.1039/d4fd00061g","url":null,"abstract":"In the domain of exchange-coupled PNTM clusters, local emergent symmetries exist which can be exploited to greatly increase the sparsity of the CI eigensolutions of such systems. Sparsity of the CI secular problem is revealed by exploring the site permutation space within spin-adapted many-body bases, and highly compressed wave functions may arise by finding optimal site orderings. However, the factorial cost of searching through the permutation space remains a bottleneck for clusters with a large number of metal centers. In this work, we explore ways to reduce the factorial scaling, by combining permutation and point group symmetry arguments, and using commutation relations between cumulative partial spin and the Hamiltonian operators, [(S<small>⁽ⁿ⁾</small>)<small>²</small>, H]. Certain site orderings lead to commuting operators, from which more sparse wave functions arise. Two graphical strategies will be discussed, one to rapidly evaluate the commutators of interest, and one in the form of a tree search algorithm to predict how many and which distinct site permutations are to be analyzed, eliminating redundancies in the permutation space. Particularly interesting is the case of the singlet spin states for which an additional reversal symmetry can be utilized to further reduce the distinct site permutations.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140797771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revisiting the driving force inducing phase separation in PEG-phosphate aqueous biphasic systems","authors":"Sophie Bonnassieux, Raj Pandya, Dhyllan Adan Skiba, Damien Degoulange, Dorothee Petit, Peter Seem, Russell Cowburn, Betar M Gallant, Alexis Jules Louis Grimaud","doi":"10.1039/d4fd00058g","DOIUrl":"https://doi.org/10.1039/d4fd00058g","url":null,"abstract":"Liquid phase separation using aqueous biphasic systems (ABS) is widely used in industrial processes for the extraction, separation and purification of macromolecules. Using water as the single solvent, a wide variety of solutes have been used to induce phase separation including polymers, ionic liquids or salts. For each system - polymer-polymer, polymer-ionic liquid, polymer-salt or salt-salt - different driving forces were proposed to induce phase separation. Specifically, for polymer-salt systems, a difference in solvation structure between the polymer-rich and the salt-rich was proposed, while other reports suggested that a large change in enthalpy and entropy accompanied the phase separation. Here, we reinvestigated the PEG/K2HPO4/H2O systems using a combination of liquid-phase nuclear magnetic resonance (NMR) and high-resolution Raman spectroscopies, coupled with injection microcalorimetry. Both NMR and Raman reveal a decreased water concentration in the PEG-rich phase, with nonetheless no significant differences observed for both 1H chemical shift or OH stretching vibrations. Hence, both PEG- and salt-rich phases exhibit similar water solvation properties, which is thus not the driving force for phase separation. Furthermore, NMR reveals a that PEG interacts with salt ions in the PEG-rich solution, inducing a downfield shift with increasing salt concentration. Injection microcalorimetry measurements were carried out to investigate any effect due to enthalpy change during mixing. Nevertheless, these measurements indicate very small enthalpy changes when mixing PEG- and salt-rich solutions in comparison with that previously recorded for salt-salt systems or associated with mixing of two solvents. Hence, our study discards any large change of enthalpy as the origin for phase separation of PEG/K2HPO4 systems, in addition to large difference in solvation properties.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140797819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stability and Structure of the Aqueous LiTFSI-LiCl Interface","authors":"Hannah Wood, Hannah M Burnett, Robert Dryfe, Paola Carbone","doi":"10.1039/d4fd00026a","DOIUrl":"https://doi.org/10.1039/d4fd00026a","url":null,"abstract":"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 the interfacial molecular structure correlates with its thermodynamic stability. We observe that at the liquid-vapour interface, TFSI− anions exhibit surfactant-like properties, leading to a reduction in surface tension and an increase in interfacial thickness. On the contrary, the interfacial stability of the LiTFSI-LiCl biphasic systems increases with the concentration of both salts, as evidenced by the increasing surface tension and decreasing interfacial thickness. The opposing effects that the ionic concentration has on the thermodynamic stability of the different interfaces are linked to the anions’ interfacial adsorption/desorption, which in turn affects the number and strength of water-water hy- drogen bonds, the interfacial molecular structure and the diffusion of cations across the interface. Finally, calculations and experiments indicate that the liquid-liquid separation is driven primarily by the concentration of LiCl, and is the result of a ’salting out’ effect.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140626828","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stabilization of lithium metal in concentrated electrolytes: effects of electrode potential and solid electrolyte interphase formation","authors":"Anusha Pradhan, Shoma Nishimura, Yasuyuki Kondo, Tomoaki Kaneko, Yu Katayama, Keitaro Sodeyama, Yuki Yamada","doi":"10.1039/d4fd00038b","DOIUrl":"https://doi.org/10.1039/d4fd00038b","url":null,"abstract":"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. In this work, we used LiN(SO<small>₂</small>F)<small>₂</small> (LiFSI) and weakly solvating 1,2-diethoxyethane (DEE) as a model electrolyte to study how its liquid structure changes upon increasing salt concentration and how it is linked to the Li plating/stripping CE. Based on previous works, we focused on Li electrode potential (<em>E</em><small>_Li</small> with reference to the redox of ferrocene) and solid electrolyte interphase (SEI) formation. Although the <em>E</em><small>_Li</small> shows a different trend in DEE as compared to conventional 1,2-dimethoxyethane (DME), which is accounted for by different ion-pairing states of Li<small>⁺</small> and FSI<small>^-</small>, the <em>E</em><small>_Li</small>-CE plots are overlapped for both electrolytes, suggesting that the <em>E</em><small>_Li</small> is one of the dominant factors of the CE. On the other hand, the extensive ion pairing results in the upward shift of FSI<small>^-</small> reduction potential, as demonstrated both experimentally and theoretically, which promotes FSI<small>^-</small>-derived inorganic SEI. Both <em>E</em><small>_Li</small> and SEI contribute to increasing the Li plating/stripping CE.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140576841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Towards Efficient Quantum Computing for Quantum Chemistry: Reducing Circuit Complexity with Transcorrelated and Adaptive Ansatz Techniques","authors":"Erika Magnusson, Aaron Fitzpatrick, Stefan Knecht, Martin Rahm, Werner Dobrautz","doi":"10.1039/d4fd00039k","DOIUrl":"https://doi.org/10.1039/d4fd00039k","url":null,"abstract":"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 their implementations in the context of variational quantum imaginary time evolution (AVQITE). The combined TC-AVQITE method is used to calculate ground state energies across the potential energy surfaces of H$_4$, LiH, and H$_2$O. In particular, H$_4$ is a notoriously difficult case where unitary coupled cluster theory, including singles and doubles excitations, fails to provide accurate results. Adding TC yields energies close to the complete basis set (CBS) limit while reducing the number of necessary operators -- and thus circuit depth -- in the adaptive ansätze. The reduced circuit depth furthermore makes our algorithm more noise-resilient and accelerates convergence. Our study demonstrates that combining the TC method with adaptive ansätze yields compact, noise-resilient, and easy-to-optimize quantum circuits that yield accurate quantum chemistry results close to the CBS limit.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140576716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mapping inorganic crystal chemical space","authors":"Hyunsoo Park, Anthony Onwuli, Keith Butler, Aron Walsh","doi":"10.1039/d4fd00063c","DOIUrl":"https://doi.org/10.1039/d4fd00063c","url":null,"abstract":"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 using compositional embedding vectors drawn from a variety of published machine-learning models. Dimensionality reduction techniques are employed to present a two-dimensional representation of inorganic crystal-chemical space, which is labelled according to whether they pass standard chemical filters and if they appear in known materials databases.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140576864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantum Embedding for Molecules with Auxiliary Particles - The Ghost Gutzwiller Ansatz","authors":"Carlos Mejuto-Zaera","doi":"10.1039/d4fd00053f","DOIUrl":"https://doi.org/10.1039/d4fd00053f","url":null,"abstract":"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 correlated solids in mind, the ghost Gutzwiller (gGut) Ansatz has been recently developed. This is a variational Ansatz which can be formulated as a self-consistent embedding approach, describing the system within a non-interacting, quasiparticle model, yet providing with accurate spectra in both low and high energy regimes. Crucially, small fragments of the system are identified as responsible for the strong correlation, and are therefore enhanced by adding a set of auxiliary orbitals, the ghosts. These capture many-body correlations through one-body fluctuations and subsequent out-projection when computing physical observables. gGut has been shown to accurately describe multi-orbital lattice models at modest computational cost. In this work, we extend the gGut framework to strongly correlated molecules, for which it holds special promise. Indeed, despite the asymmetric embedding treatment, the quasiparticle Hamiltonian effectively describes all major sources of correlation in the molecule: strong correlation through the ghosts in the fragment, and dynamical correlation through the quasiparticle description of its environment. To adapt the gGut Ansatz for molecules, we address the fact that, unlike in the lattice model previously considered, electronic interactions in molecules are not local. Hence, we explore a hierarchy of approximations of increasing accuracy capturing interactions between fragments and environment, and within the environment, and discuss how these affect the embedding description of correlations in the whole molecule. We will compare the accuracy of the gGut model with established methods to capture strong correlation within active space formulations, and assess the realistic use of this novel approximation to the theoretical description of correlated molecular clusters.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140577127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"What can Quantum Information Theory Offer to Quantum Chemistry?","authors":"Damiano Aliverti-Piuri, Kaustav Chatterjee, Lexin Ding, Ke Liao, Julia Liebert, Christian Schilling","doi":"10.1039/d4fd00059e","DOIUrl":"https://doi.org/10.1039/d4fd00059e","url":null,"abstract":"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 correlation. We then demonstrate that particle correlation equals orbital correlation minimized with respect to all orbital reference bases. Accordingly, particle correlation resembles the minimal, thus intrinsic, complexity of many-electron wavefunctions while orbital correlation quantifies their complexity relative to a basis. We illustrate these novel concepts of intrinsic and extrinsic correlation complexity with analytic and numerical examples, which also demonstrates the crucial link between the two correlation pictures. Our results provide theoretical justification for the long-favored natural orbitals for simplifying electronic structures, and open new pathways for developing more efficient approaches towards the electron correlation problem.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140576714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Orbital optimisation in xTC transcorrelated methods","authors":"Daniel Kats, Evelin Martine Corvid Christlmaier, Thomas Schraivogel, Ali Alavi","doi":"10.1039/d4fd00036f","DOIUrl":"https://doi.org/10.1039/d4fd00036f","url":null,"abstract":"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 of these methods in comparison to standard xTC methods is demonstrated, and the advantages and disadvantages of the orbital optimisation are discussed.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140576712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}