Article
Materials Science, Multidisciplinary
Mai Ye, Xianghan Xu, Xiangyue Wang, Jaewook Kim, Sang-Wook Cheong, Girsh Blumberg
Summary: In this study, we investigate the ground-state properties, electronic excitations, and lattice dynamics in the spin-liquid candidate TbInO3 using polarization-resolved Raman spectroscopy. We identify the ground state of Tb3+ ions as a non-Kramers doublet and establish the low-energy crystal-field level scheme. The enhanced linewidth of crystal-field modes is linked to magnetic fluctuations near the spin-liquid ground state, and specific-heat data supports the obtained crystal-field level scheme.
Article
Chemistry, Physical
Angel Albavera-Mata, S. B. Trickey, Richard G. Hennig
Summary: This study demonstrates a method for improving the accuracy of calculating spin-crossover energies, and proposes a set of recommended averaged Ueff values for high-throughput calculations.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Review
Chemistry, Multidisciplinary
Kuppusamy Senthil Kumar, Mario Ruben
Summary: This review covers the advances in vacuum-sublimable SCO complexes, including the design and synthesis of functional SCO complexes, on-surface SCO of thin films, and various device architectures based on sublimable SCO complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Hongyan Chen, Hung-Hsiang Yang, Timo Frauhammer, Haoran You, Qing Sun, Peter Nagel, Stefan Schuppler, Ana Belen Gaspar, Jose Antonio Real, Wulf Wulfhekel
Summary: Spin crossover (SCO) complexes are sensitive to changes in the environment and can change the spin of the central metallic ion, making them ideal for molecular spintronics. However, when SCO complexes are deposited on ferromagnetic surfaces, the interaction between the molecules and the surface blocks spin-state switching. This study investigates the behavior of a Fe(II) SCO complex on a passivated ferromagnetic film, showing thermal spin crossover and a sizable exchange interaction with the ferromagnetic substrate. These findings provide a feasible design strategy for SCO-ferromagnetic hybrid devices.
Review
Chemistry, Inorganic & Nuclear
Mohammad Khurram Javed, Arshia Sulaiman, Masahiro Yamashita, Zhao-Yang Li
Summary: The spin crossover (SCO) phenomenon has made remarkable progress in applications, particularly in materials exhibiting SCO-luminescence synergy. This review aims to provide an overview of the luminescent and magnetic properties of SCO materials, synthesis strategies, and progress made in constructing such materials over the years.
COORDINATION CHEMISTRY REVIEWS
(2022)
Review
Chemistry, Multidisciplinary
Ramon Torres-Cavanillas, Miguel Gavara-Edo, Eugenio Coronado
Summary: The field of spin-crossover complexes is transitioning from studying the spin transition phenomenon to its application in molecular electronics. Processing spin-crossover materials as nanoparticles is a convenient way to maintain the bistability and reduce size. This paper reviews the recent advances in the chemical design of these nanoparticles and their integration into electronic devices, while also focusing on integrating them with 2D materials to improve device endurance and spin state detection.
ADVANCED MATERIALS
(2023)
Review
Chemistry, Physical
Saikat Mukherjee, Dmitry A. Fedorov, Sergey A. Varganov
Summary: This article reviews the application of nonadiabatic molecular dynamics methods in modeling spin-crossover transitions, focusing on different representations of electronic states, interstate couplings, and various NAMD methods used. Representative applications, as well as fundamental questions related to spin processes, are also discussed, with suggestions for future methodological developments in NAMD.
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, VOL 72
(2021)
Article
Materials Science, Multidisciplinary
Haining Pan, Sankar Das Sarma
Summary: The study explores the properties of the superconductor-semiconductor nanowire hybrid Majorana platform in the presence of a deterministic slowly varying inhomogeneous chemical potential and a random quenched potential disorder. By calculating the tunnel conductance, the research examines the crossover among different mechanisms, with findings indicating the dominant role of random disorder in experiments.
Article
Chemistry, Multidisciplinary
Maria Jose Heras Ojea, Jeff M. Van Raden, Shayan Louie, Richard Collins, Daniel Pividori, Jordi Cirera, Karsten Meyer, Ramesh Jasti, Richard A. Layfield
Summary: The addition of bipyridyl-embedded cycloparaphenylene nanohoop to an iron(II) complex leads to a distorted octahedral structure with spin-crossover behavior. Computational studies suggest that the size and curvature of the nanohoop play a critical role in determining the SCO properties of the iron(II) complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Chenyang Li, Francesco A. Evangelista
Summary: This study presents a spin-free formulation of the multireference driven similarity renormalization group based on ensemble normal ordering, which is used to compute constants of diatomic molecules and spin splittings of transition-metal complexes, demonstrating that third-order perturbative corrections are essential for achieving reasonably converged energetics. The results suggest good agreement with local CC theory, highlighting the importance of spin-free quantities in accurately predicting molecular properties.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Sven Johannsen, Sascha Ossinger, Troels Markussen, Felix Tuczek, Manuel Gruber, Richard Berndt
Summary: The behavior of spin crossover compound on a silver surface was investigated, revealing that two molecules in tetramers can switch states by current injection with significantly higher yields compared to other systems. The other two molecules remain unchanged, but can be used as contacts for switching neighboring molecules. A model of tetramer structure was proposed and validated through experiments.
Article
Chemistry, Inorganic & Nuclear
Yurii S. Bibik, Sergiu Shova, Aurelian Rotaru, Sergii I. Shylin, Igor O. Fritsky, Rostyslav D. Lampeka, Il'ya A. Gural'skiy
Summary: This paper describes a new 2D coordination polymer with hysteretic spin crossover behavior, which exhibits attractive features such as thermochromism, stability upon thermal cycling, and significant volume expansion during the spin crossover process.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Teresa Delgado, Melanie Villard
Summary: Spin crossover materials can switch between high spin and low spin states, with different properties. The spin transition can be tracked using various techniques. Conducting a laboratory experiment on thermal transition provides a simple way to understand fundamental concepts and engage in materials synthesis and characterization.
JOURNAL OF CHEMICAL EDUCATION
(2022)
Review
Chemistry, Multidisciplinary
Lalminthang Kipgen, Matthias Bernien, Felix Tuczek, Wolfgang Kuch
Summary: This article summarizes the research on spin-crossover molecules on solid surfaces in molecular spintronics, covering a range from single molecules to ultrathin films, mainly in the sub-10 nm range. The achievements, challenges, and prospects in this field are highlighted.
ADVANCED MATERIALS
(2021)
Article
Nanoscience & Nanotechnology
Xianglian Song, Sina Abedini Dereshgi, Edgar Palacios, Yuanjiang Xiang, Koray Aydin
Summary: The study shows that using hexagonal boron nitride and gold as materials can achieve efficient absorption and band stop filtering effects in the mid-infrared region. Experiments have yielded modal interactions with high coupling strengths in the mid-infrared region. Additionally, the interaction between optical phonon modes and plasmonic modes has also been studied.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Inorganic & Nuclear
Sophia Klokishner, Serghei Ostrovsky, Andrew Palii, Boris Tsukerblat
Summary: This article provides a brief overview of the theoretical modeling of spin transitions in polymetallic compounds. Unlike many other reviews, this work focuses on the nature of cooperative interaction among metal clusters in molecular crystals, with an emphasis on the physical role of molecular vibrations and phonons. The suggested model demonstrates a satisfactory description of observed spin transitions in various compounds.
Article
Chemistry, Physical
Shmuel Zilberg, Yaniv Stekolshik, Andrew Palii, Boris Tsukerblat
Summary: In this study, the controllable electron transfer in mixed-valence systems was investigated computationally. The electron transfer in a series of oxidized norbornadiene and its derivatives was studied. The through-space effect was found to be the major factor in electron transfer at short distances between the redox centers, while the through-bond contribution dominated at long distances.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Boris Tsukerblat, Andrew Palii, Shmuel Zilberg, Denis Korchagin, Sergey Aldoshin, Juan Modesto Clemente-Juan
Summary: This article examines the ability of using a square-planar cell composed of one-electron mixed valence dimers to function in quantum cellular automata (QCA) when the intracell Coulomb interaction U is not extremely strong. By considering strong vibronic coupling, the study demonstrates that a significant barrier can be created between two diagonal-type charge configurations, ensuring bistability and polarizability of the cells even without a sufficient Coulomb barrier.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Inorganic & Nuclear
Andrew Palii, Sergey Aldoshin, Boris Tsukerblat
Summary: This study discusses the problem of electron transfer in mixed valence molecules, which is crucial for the functioning of molecular Quantum Cellular Automata (QCA). A theoretical model of tetrameric bi-electronic mixed valence molecular square is presented, taking into account interelectronic Coulomb repulsion, vibronic coupling, and electron transfer between neighboring redox sites. The results show that key features of QCA cells, such as bistability and switchability, can be achieved even when the Coulomb repulsion is not significantly stronger than the electron transfer energy, as long as the vibronic coupling is sufficiently strong.
Article
Chemistry, Physical
Sophia Klokishner, Serghei Ostrovsky
Summary: This study proposes a model to explain the spin transformation in crystals containing linear trinuclear iron(II) clusters and explores the different types of spin transitions that trinuclear systems may exhibit. The effects of external pressure on the spin transitions are also discussed, focusing on the Fe3(bntrz)6(tcnset)6 compound.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Andrew Palii, Denis Korchagin, Ksenya Kondrina, Sergey Aldoshin, Shmuel Zilberg, Boris Tsukerblat
Summary: This study generalizes the theory of magnetic coupling between localized spins to a trigonal, six-center, four-electron molecule with partial valence delocalization. The combination of electron transfer within the valence-delocalized subsystem and interatomic exchange leads to a special kind of double exchange (DE) called external core double exchange (ECDE). The study compares the effect of ECDE on the ground spin state of the trigonal molecule with the effect produced by DE in a four-electron, mixed-valence (MV) trimer. The results show a high diversity of ground spin states depending on the relative magnitudes and signs of transfer and exchange parameters, suggesting potential applications in molecular electronics and spintronics.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Shmuel Zilberg, Boris Tsukerblat, Andrew Palii
Summary: By studying the cation-radical form of 1,4-diallyl-butane and its derivatives, we found that the electron transfer barrier in compounds with a π-fragment on the bridge is higher compared to those with a saturated bridge. We proposed a model based on the specific polaronic effect of the spacer, which can provide a route to controllable electron transfer in bridged mixed-valence compounds.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Andrew Palii, Valeria Belonovich, Sergei Aldoshin, Shmuel Zilberg, Boris Tsukerblat
Summary: In this article, the power dissipation in nonadiabatic switching events in mixed-valence molecular cells of quantum cellular automata (QCA) is analyzed. The study shows that while there is a competition between the requirements for a strong nonlinear response and low heat release, it is possible to achieve functional advantages and practical application of QCA through molecular design.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Oleg Reu, Serghei Ostrovsky, Sophia Klokishner
Summary: The charge-transfer-induced spin transition of the cyanide-bridged tetranuclear complex [Co2Fe2(bpy*)(4)(CN)(6)(tp*)(2)](PF6)(2)-2CP-8BN has been studied using DFT calculations of single-point energies at various temperatures. The results reveal the spin conversion process of the compound and show that different spin states are present at different temperatures. The findings are consistent with experimental data on magnetic susceptibility, and the potential for predicting spin transitions in new materials based on DFT calculations is discussed.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Andrew Palii, Valeria Belonovich, Boris Tsukerblat
Summary: The impacts of electronic and vibronic interactions on the specific heat release during the nonadiabatic switching of electric field polarization in a one-electron mixed-valence dimer are analyzed using the Piepho-Krausz-Schatz vibronic model. The study aims to find an optimal parameter regime to minimize heat release while maintaining a strong nonlinear response of the dimer to the electric field. Quantum mechanical vibronic calculations reveal that a weak electric field, combined with weak vibronic coupling and/or strong electron transfer, leads to minimal heat release, but it is incompatible with the requirement of a strong nonlinear response. On the contrary, molecules with strong vibronic interactions and/or weak transfer exhibit a rather strong nonlinear response even under a very weak electric field, ensuring low heat release.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Yulia P. P. Tupolova, Vladimir E. E. Lebedev, Denis V. V. Korchagin, Valery V. V. Tkachev, Andrey N. N. Utenyshev, Roman B. B. Morgunov, Andrei V. V. Palii, Igor N. N. Shcherbakov, Sergey M. M. Aldoshin
Summary: A hexacoordinated Co(ii) complex of [CoL(NCS)(2)]center dot 2DMSO (1) has been synthesized and characterized. The Co(ii) coordination polyhedron is distorted towards trigonal prismatic symmetry due to the helix-like distortion of the complex. Complex 1 shows slow magnetization relaxation in an applied DC magnetic field of 1000 Oe, which is well described by the Raman mechanism. The performed CASSCF+NEVPT2 calculations provide clear insight into the origin of the magnetic anisotropy in 1.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Maxim G. Chegerev, Denis Korchagin, Gennady Shilov, Nikolay N. Efimov, Andrey G. Starikov, Alexandr Piskunov, Anatoly Chernyshev, Aleksei N. Bulgakov, Vladimir Minkin, Andrei Palii, Sergey M. Aldoshin
Summary: This paper reports the synthesis and magnetic characterization of a family of cobalt-dioxolene complexes. Three complexes, including a neutral complex 1, an ionic complex 2, and an ionic complex 3, were synthesized and characterized. The structures and magnetic behaviors of these complexes were investigated.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Alberto M. Ruiz, Dorye L. Esteras, Andrey Rybakov, Jose J. Baldovi
Summary: This study investigates the crystal, electronic and magnetic structures of selenized Janus monolayers based on MnPS3 and NiPS3, and predicts the enhancement of magnetic anisotropy and the emergence of large Dzyaloshinskii-Moriya interactions.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
E. A. Yureva, D. V. Korchagin, A. A. Anichkin, G. V. Shilov, K. A. Babeshkin, N. N. Efimov, A. V. Palii, S. M. Aldoshin
Summary: Here, we report the synthesis, structure, and magnetic properties of a four-coordinate mononuclear Co(ii) diiodide complex with the 3,5-dimethylpyrazole ligand. The complex exhibits a strong easy-axis-type magnetic anisotropy and demonstrates slow relaxation of magnetization at zero dc field.
DALTON TRANSACTIONS
(2022)