Unraveling the Contributions to Spin–Lattice Relaxation in Kramers Single-Molecule Magnets

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(50), P. 22965 - 22975

Published: Dec. 9, 2022

The study of how spin interacts with lattice vibrations and relaxes to equilibrium provides unique insights into its chemical environment the relation between electronic structure molecular composition. Despite importance for several disciplines, ranging from magnetic resonance quantum technologies, a convincing interpretation dynamics in crystals molecules is still lacking due challenging experimental determination correct relaxation mechanism. We apply ab initio series 12 coordination complexes Co2+ Dy3+ ions selected among ∼240 compounds that largely cover literature on single-molecule magnets well represent different regimes relaxation. Simulations reveal Orbach rate known mostly depends ions' zero-field splitting little details vibrations. Raman instead found be also significantly affected by features low-energy phonons. These results provide complete understanding factors limiting lifetime revisit years investigations making it possible transparently distinguish mechanisms.

Language: Английский

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The critical role of ultra-low-energy vibrations in the relaxation dynamics of molecular qubits

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: March 24, 2023

Abstract Improving the performance of molecular qubits is a fundamental milestone towards unleashing power magnetism in second quantum revolution. Taming spin relaxation and decoherence due to vibrations crucial reach this milestone, but hindered by our lack understanding on nature their coupling spins. Here we propose synergistic approach study prototypical qubit. It combines inelastic X-ray scattering measure phonon dispersions along main symmetry directions crystal dynamics simulations based DFT. We show that canonical Debye picture lattice breaks down intra-molecular with very-low energies 1-2 meV are largely responsible for up ambient temperature. identify origin these modes, thus providing rationale improving coherence. The flexibility open new avenues investigation magnetic molecules potential removing roadblocks toward use devices.

Language: Английский

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Unravelling the role of spin–vibrational coupling in designing high-performance pentagonal bipyramidal Dy(iii) single ion magnets

Chemical Science, Journal Year: 2024, Volume and Issue: 15(17), P. 6465 - 6477

Published: Jan. 1, 2024

Detailed DFT and ab initio calculations unveil the correlation between spin–phonon vibrations blocking temperature to provide design clues improve single-ion magnet characteristics in pseudo- D 5h family of Dy( iii ) SMMs.

Language: Английский

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Organolanthanide Single‐Molecule Magnets with Heterocyclic Ligands

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: July 2, 2024

Lanthanide (Ln) based mononuclear single-molecule magnets (SMMs) provide probably the finest ligand regulation model for magnetic property. Recently, development of such SMMs has witnessed a fast transition from coordination to organometallic complexes because latter provides fertile, yet not fully excavated soil SMMs. Especially those with heterocyclic ligands have shown potential reach higher blocking temperature. In this minireview, we give an overview design principle and highlight "shining stars" organolanthanide on ring sizes ligands, analysing how electronic structures stiffness subsequently formed molecules affect dynamic magnetism Finally, envisaged future Ln-SMMs.

Language: Английский

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Theoretical Study of Pentacoordinated Lanthanide Single-Ion Magnets via Ab Initio Electronic Structure Calculation

Magnetochemistry, Journal Year: 2025, Volume and Issue: 11(1), P. 3 - 3

Published: Jan. 7, 2025

A theoretical study, based on ab initio electronic structure calculation, is performed in a group of 16 pentacoordinate Dy-SIMs. Theoretical results provide reasonable explanation the observed SMM performance concise criterion, i.e., co-existence long τQTM and high Ueff. To have desired favoring good performance, contribution from equatorial coordinating atoms might be even more important than that axial atoms. Widening ∠O–Dy–O probable way to improve pentacoordinated Starting existing systems, rigid-scan type exploration indicates possibility Ueff higher 1600 K.

Language: Английский

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A machine-learning framework for accelerating spin-lattice relaxation simulations

npj Computational Materials, Journal Year: 2025, Volume and Issue: 11(1)

Published: March 6, 2025

Molecular and lattice vibrations are able to couple the spin of electrons lead their relaxation decoherence. Ab initio simulations have played a fundamental role in shaping our understanding this process but further progress is hindered by high computational cost. Here we present an accelerated framework based on machine-learning models for prediction molecular spin-phonon coupling coefficients. We apply method three open-shell coordination compounds exhibiting long times show that approach achieves semi-to-full quantitative agreement with ab methods reducing cost about 80%. Moreover, naturally extends dynamics simulations, paving way study condensed matter beyond simple equilibrium harmonic thermal baths.

Language: Английский

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Get under the Umbrella: A Comprehensive Gateway for Researchers on Lanthanide‐Based Single‐Molecule Magnets

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(35)

Published: July 7, 2023

Abstract The number of scientific articles that need to be considered cover a research topic is ever‐increasing and quite difficult for newcomer assimilate. This particularly true in dynamic discipline like Molecular Magnetism. In order help young researchers this field, article proposes “review reviews” also known as an “umbrella review” on lanthanide‐based single‐molecule magnets ( 4 f ‐SMM). As preamble, various bibliographic search techniques AI‐based tools search, indexing, summarization are proposed commented. Then, the main milestones ‐SMM identified. core paper, books, book articles, reviews dealing with contextualized classified by subtopics. therefore gateway field.

Language: Английский

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Spin-Phonon Relaxation in Magnetic Molecules: Theory, Predictions and Insights

Challenges and advances in computational chemistry and physics, Journal Year: 2023, Volume and Issue: unknown, P. 219 - 289

Published: Jan. 1, 2023

Language: Английский

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Ab initioprediction of key parameters and magneto-structural correlation of tetracoordinated lanthanide single-ion magnets

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(27), P. 18387 - 18399

Published: Jan. 1, 2023

Single-molecule magnets (SMMs) have great potential in becoming revolutionary materials for micro-electronic devices. As one type of SMM and holding the performance record, lanthanide single-ion (Ln-SIMs) stand at forefront family. Lowering coordination number (CN) is an important strategy to improve Ln-SIMs. Here, we report a theoretical study on typical group low-CN Ln-SIMs, i.e., tetracoordinated structures. Our results are consistent with those experiments they identify same three best Ln-SIMs via concise criterion, co-existence long τQTM high Ueff. Compared record-holding dysprosocenium systems, SIMs here possess values that shorter by several orders magnitude Ueff lower ∼1000 Kelvin (K). These reasons fact clearly inferior dysprosocenium. A simple but intuitive crystal-field analysis leads routes given Ln-SIM, including compression axial bond length, widening angle, elongation equatorial length usage weaker donor ligands. Although these not brand-new, most efficient option degree improvement resulting from it known advance. Consequently, magneto-structural study, covering various routes, carried out Ln-SIM route shown be ∠O-Dy-O angle. The optimistic case, having 180°, could (up 103 s) (∼2400 K) close record-holders. Subsequently, blocking temperature (TB) 64 K predicted possible it. more practical being 160°, up 400 s, around 2200 possibility TB 57 K. inherent precision limit, predictions provide guide improvement, starting existing system.

Language: Английский

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Nanostructured Design Cathode Materials for Magnesium-Ion Batteries

ACS Omega, Journal Year: 2024, Volume and Issue: 9(4), P. 4229 - 4245

Published: Jan. 19, 2024

Energy is undeniably one of the most fundamental requirements current generation. Solar and wind energy are sustainable renewable sources; however, their unpredictability points to development storage systems (ESSs). There has been a substantial increase in use batteries, particularly lithium-ion batteries (LIBs), as ESSs. However, low rate capability degradation due electric load long-range vehicles pushing LIBs limits. As alternative ESSs, magnesium-ion (MIBs) possess promising properties advantages. Cathode materials play crucial role MIBs. In this regard, variety cathode materials, including Mn-based, Se-based, vanadium- vanadium oxide-based, S-based, Mg

Language: Английский

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