Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Chemical Reviews, Год журнала: 2018, Номер 118(15), С. 7026 - 7068

Опубликована: Май 16, 2018

Nonadiabatic mixed quantum–classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution nonadiabatic phenomena molecules and supramolecular assemblies. NA-MQC is characterized by partition molecular system into two subsystems: one be treated mechanically (usually but not restricted electrons) another dealt with classically (nuclei). The subsystems are connected through couplings terms enforce self-consistency. A local approximation underlies classical subsystem, implying that direct can simulated, without needing precomputed potential energy surfaces. split allows reducing costs, enabling treatment realistic systems diverse fields. Starting from three most well-established methods—mean-field Ehrenfest, trajectory surface hopping, multiple spawning—this review focuses on programs developed last 10 years. It stresses relations between their domains application. electronic structure commonly used together reviewed as well. accuracy precision simulations critically discussed, general guidelines choose an adequate method for each application delivered.

Язык: Английский

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Proton-Coupled Electron Transfer Guidelines, Fair and Square

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(2), С. 560 - 576

Опубликована: Янв. 6, 2021

Proton-coupled electron transfer (PCET) reactions are fundamental to energy transformation in natural and artificial systems increasingly recognized areas such as catalysis synthetic chemistry. The interdependence of proton brings a mechanistic richness reactivity, including various sequential concerted mechanisms. Delineating between different PCET mechanisms understanding why particular mechanism dominates crucial for the design optimization that use PCET. This Perspective provides practical guidelines how discern based on interpretations thermodynamic data with temperature-, pressure-, isotope-dependent kinetics. We present new PCET-zone diagrams show can switch or even be eliminated by varying (ΔGPT° ΔGET°) coupling strengths system. discuss appropriateness asynchronous rationalize observations organic reactions, distinction hydrogen atom other reactions. Contemporary issues future prospects research discussed.

Язык: Английский

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A bio-inspired coordination polymer as outstanding water oxidation catalyst via second coordination sphere engineering

Nature Communications, Год журнала: 2019, Номер 10(1)

Опубликована: Ноя. 7, 2019

Abstract First-row transition metal-based catalysts have been developed for the oxygen evolution reaction (OER) during past years, however, such typically operate at overpotentials ( η ) significantly above thermodynamic requirements. Here, we report an iron/nickel terephthalate coordination polymer on nickel form NiFeCP/NF as catalyst OER, in which both coordinated and uncoordinated carboxylates were maintained after electrolysis. exhibits outstanding electro-catalytic OER activity with a low overpotential of 188 mV 10 mA cm −2 1.0 KOH, small Tafel slope excellent stability. The pH-independent reversible hydrogen electrode scale suggests that concerted proton-coupled electron transfer (c-PET) process is rate-determining step (RDS) water oxidation. Deuterium kinetic isotope effects, proton inventory studies atom-proton-transfer measurements indicate are serving relays, similar function amino acid residues photosystem II (PSII), accelerating proton-transfer rate.

Язык: Английский

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Brønsted–Lowry Acid Strength of Metal Hydride and Dihydrogen Complexes

Chemical Reviews, Год журнала: 2016, Номер 116(15), С. 8588 - 8654

Опубликована: Март 10, 2016

Transition metal hydride complexes are usually amphoteric, not only acting as donors, but also Brønsted-Lowry acids. A simple additive ligand acidity constant equation (LAC for short) allows the estimation of acid dissociation Ka(LAC) diamagnetic transition and dihydrogen complexes. It is remarkably successful in systematizing diverse reports over 450 reactions acids with bases hydrides complexes, including catalytic cycles where these proposed or observed. There links between pKa(LAC) pKa(THF), pKa(DCM), pKa(MeCN) neutral cationic For groups from chromium to nickel, tables provided that order most acidic (pKa(LAC) -18) least 50). Figures constructed showing above solvent pKa scales organic below summarize a large amount information. Acid-base features analyzed catalysts gold ionic hydrogenations, bifunctional hydrogen oxidation evolution electrocatalysis, H/D exchange, olefin hydrogenation isomerization, ketones, aldehydes, imines, carbon dioxide, hydrogenases their model palladium intermediates.

Язык: Английский

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Bioinspiration in light harvesting and catalysis

Nature Reviews Materials, Год журнала: 2020, Номер 5(11), С. 828 - 846

Опубликована: Авг. 7, 2020

Язык: Английский

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Atom Tunneling in Chemistry

Angewandte Chemie International Edition, Год журнала: 2016, Номер 55(18), С. 5400 - 5413

Опубликована: Март 16, 2016

Quantum mechanical tunneling of atoms is increasingly found to play an important role in many chemical transformations. Experimentally, atom-tunneling can be indirectly detected by temperature-independent rate constants at low temperature or enhanced kinetic isotope effects. On the contrary, using computational investigations influence on reaction rates directly monitored. The tunnel effect, for example, changes paths and branching ratios, enables reactions astrochemical environment that would impossible thermal transition, influences biochemical processes.

Язык: Английский

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Pulsed Laser in Liquids Made Nanomaterials for Catalysis

Chemical Reviews, Год журнала: 2021, Номер 121(13), С. 7568 - 7637

Опубликована: Июнь 2, 2021

Catalysis is essential to modern life and has a huge economic impact. The development of new catalysts critically depends on synthetic methods that enable the preparation tailored nanomaterials. Pulsed laser in liquids synthesis can produce uniform, multicomponent, nonequilibrium nanomaterials with independently precisely controlled properties, such as size, composition, morphology, defect density, atomistic structure within nanoparticle at its surface. We cover fundamentals, unique advantages, challenges, experimental solutions this powerful technique review state-of-the-art laser-made electrocatalysts for water oxidation, oxygen reduction, hydrogen evolution, nitrogen carbon dioxide organic oxidations, followed by light-driven catalytic processes heterogeneous catalysis thermochemical processes. also highlight laser-synthesized which proposed applications exist. This provides practical guide how community capitalize pulsed advance catalyst development, leveraging synergies two fields intensive research.

Язык: Английский

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Second and Outer Coordination Sphere Effects in Nitrogenase, Hydrogenase, Formate Dehydrogenase, and CO Dehydrogenase

Chemical Reviews, Год журнала: 2022, Номер 122(14), С. 11900 - 11973

Опубликована: Июль 18, 2022

Gases like H

Язык: Английский

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Surface Sulfate Ion on CdS Catalyst Enhances Syngas Generation from Biopolyols

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(17), С. 6533 - 6541

Опубликована: Апрель 27, 2021

Photocatalytic biomass conversion represents an ideal way of generating syngas because the sustainable use carbon and solar energy. However, lack efficient electron–proton transfer limits its efficiency. We here report unprecedented method to simultaneously increase both electron proton by creating surface sulfate ions on CdS catalyst ([SO4]/CdS). Surface ion [SO4] is bifunctional, serving as acceptor promote transfer, increasing oxidation potential valence band enhance transfer. [SO4]/CdS produces a mixture from glycerol without CO2. Compared with pristine CdS, exhibits 9-fold higher CO generation rate (0.31 mmol g–1 h–1) 4-fold H2 (0.05 h–1). A wide range sugars, such glucose, fructose, maltose, sucrose, xylose, lactose, insulin, starch, were facilely converted into syngas. This study reports pivotal effect in photocatalysis provides facile for photocatalytic

Язык: Английский

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Molecular Catalysts with Diphosphine Ligands Containing Pendant Amines

Chemical Reviews, Год журнала: 2022, Номер 122(14), С. 12427 - 12474

Опубликована: Май 31, 2022

Pendant amines play an invaluable role in chemical reactivity, especially for molecular catalysts based on earth-abundant metals. As inspired by [FeFe]-hydrogenases, which contain a pendant amine positioned cooperative bifunctionality, synthetic have been developed to emulate this multifunctionality through incorporation of the second coordination sphere. Cyclic diphosphine ligands containing two serve as basis class that extensively studied and used demonstrate impact base. These 1,5-diaza-3,7-diphosphacyclooctanes, now often referred "P2N2" ligands, profound effects reactivity many catalysts. The resulting [Ni(PR2NR′2)2]2+ complexes are electrocatalysts both oxidation production H2. Achieving optimal benefit requires it has suitable basicity is properly relative metal center. In addition catalytic efficacy demonstrated with H2, also several metals different reactions, solution immobilized surfaces. catalyst design continues expand.

Язык: Английский

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