Review
Multidisciplinary Sciences
Isaac B. Bersuker
Summary: This paper discusses the relationship between symmetry, broken symmetry, and spontaneous broken symmetry of polyatomic systems with Jahn-Teller and pseudo-Jahn-Teller effects, highlighting the importance of nonadiabaticity in the interaction between electrons and nuclei. An improved definition of stereo-chemical polyatomic space configuration is suggested, and the role of JTEs in producing novel properties in atomic systems is emphasized. The Curie principle is shown to play a key role in observing spontaneous symmetry breaking in matter, leading to the discovery of new properties such as ferroelectricity and orientational polarization.
Article
Chemistry, Inorganic & Nuclear
Sa Yao, Clement Falaise, Soumaya Khlifi, Nathalie Leclerc, Mohamed Haouas, David Landy, Emmanuel Cadot
Summary: The study demonstrates that the interaction strength between gamma-CD and oxidized or one-electron reduced POMs decreases as the global ionic charge of the POM unit increases. The addition/removal of one electron to POMs, particularly those with molybdenum and vanadium addenda, allows for tuning the host-guest association strength, offering a new avenue for the design of smart materials through redox stimuli.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Oleg A. Vasilyev, Krishna R. Nandipati, Ilya S. Navarkin, Victor G. Solomonik, Wolfgang Domcke
Summary: The study investigates the strong Jahn-Teller and pseudo-Jahn-Teller effects in niobium tetrafluoride, revealing detailed characteristics of molecular structures through complex numerical analysis. By constructing a coupling Hamiltonian and calculating vibrational spectra, the importance of coupling effects and their impact near potential energy surface crossings are identified.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Andrew Palii, Valeria Belonovich, Sergey Aldoshin, Boris Tsukerblat
Summary: A multimode vibronic model is used to analyze the localization-delocalization phenomenon in the two-electron square-planar mixed valence cluster. The dominant coupling with B1g vibration results in the electronic pair being localized on the diagonals of the square, while the dominant coupling with A1g mode leads to fully delocalized electronic pair.
Article
Chemistry, Multidisciplinary
Sebastian Mai, Marcus Holzer, Anastasia Andreeva, Leticia Gonzalez
Summary: The study derived heuristic rules to identify preferred mixed-valence isomers and Jahn-Teller axis arrangements in water oxidation catalysts, finding that different oxidation states localize on different Mn centers and quickly interconvert between different Jahn-Teller axis arrangements, leading to averaged bond lengths in the crystal structure. The combination of chemically inert cubane-vanadate bonds, activatable cubane-acetate/water bonds, and low activation barriers for intramolecular rearrangement of Jahn-Teller axes plays a key role in the reactivity of these compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Takuya Kodama, Mitsuya Aoba, Yasukazu Hirao, Samara Medina Rivero, Juan Casado, Takashi Kubo
Summary: This study reports the preparation and characterization of a through-space conjugated multi-phenalenyl triradical. The investigation shows that the triradical can exist in two forms- an acute form in solution state and a preferred obtuse form in solid state, and these two forms can be reversibly interconverted by thermal energy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Artem L. L. Khoroshilov, Kirill M. M. Krasikov, Andrey N. N. Azarevich, Alexey V. V. Bogach, Vladimir V. V. Glushkov, Vladimir N. N. Krasnorussky, Valery V. V. Voronov, Natalya Y. Y. Shitsevalova, Volodymyr B. B. Filipov, Slavomir Gabani, Karol Flachbart, Nikolay E. E. Sluchanko
Summary: The charge transport in the paramagnetic phase of Ho0.8Lu0.2B12 was studied, revealing the existence of an anomalous Hall effect due to the instability of the fcc lattice and the electronic structure. The Hall effect was observed in four mono-domain single crystals of Ho0.8Lu0.2B12 with different crystal axis orientations. An intrinsic anisotropic positive Hall resistivity was found at low temperatures, along with a negative Hall resistivity at high magnetic fields. The anomalies in the resistivity tensor components were explained as the formation of fluctuating charge chains in the structure, with intrinsic and extrinsic mechanisms contributing to the Hall effect. Additionally, a ferromagnetic contribution from magnetic polarization of 5d states was observed in the Hall signal.
Article
Chemistry, Physical
Minggang Guo, Zhifan Wang, Fan Wang
Summary: This study analyzed the structural characteristics of cyclic C3H3 using various computational methods and found that the structure with Cs symmetry is the only stable configuration, while other structures are second-order saddle points or transition states.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Physics, Condensed Matter
Xiaoxu Bao, Juyi Wang, Xianfeng Wu, Chunyan He, Hao Luo, Qiligeer Bai, Vrhn Bao, Yulong Bai, Junjie Liu, Shifeng Zhao
Summary: This study investigates the magnetic properties and magnetocaloric effects of polycrystalline Bi0.3xLaxCa0.7MnO3 (x = 0, 0.1, 0.2) ceramics, using Raman active modes and phonons to detect charge disorder and local structure distortion. The large magnetocaloric effect is explained by Jahn-Teller distortion and valence perturbations induced by La doping. The study also reveals a connection between complex magnetic phase transition and magnetic entropy in doped manganites, attributed to the temperature-dependent competition between orbital order and charge order.
PHYSICA B-CONDENSED MATTER
(2023)
Article
Chemistry, Multidisciplinary
Ines Sanchez-Movellan, David Carrasco-Busturia, Juan M. Garcia-Lastra, Pablo Garcia-Fernandez, Jose A. Aramburu, Miguel Moreno
Summary: This study investigates the pressure-induced switch of the long axis of MnF63- units in monoclinic Na3MnF6 compound and Mn3+-doped Na3FeF6 through first principles calculations. The results show that the switch is caused by the anisotropic response of the low symmetry lattice to hydrostatic pressure, rather than the static Jahn-Teller effect. This work provides insights into the effects of pressure on low symmetry insulating compounds containing d(4) or d(9) ions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Korutla Srikanth, Abhishek Kumar, Rajagopala Rao Tammineni
Summary: The first five low-lying electronic states of HCPN3 were investigated through extensive ab initio electronic structure and quantum dynamics studies to reproduce the 193 nm photoelectron spectrum. A vibronic Hamiltonian was constructed for time-dependent and time-independent quantum dynamical studies, revealing interesting nonadiabatic effects due to numerous conical intersections and crossings among electronic states. The theoretical bands corresponding to the five electronic states reproduced all three experimental spectral bands, with satisfying agreement between the calculated results and experimental data.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Hong-Lei Xu, Chad Studvick, Chao Liu, Yuan Xue, Ivan A. Popov, Zhong-Ming Sun
Summary: An unexpected single-metal-filled double-cage cluster has been reported, representing the largest group 14 intermetalloid cluster encapsulating a single transition metal atom. The structural characteristic of the cluster is described, and the deviation of the central atom is discussed in terms of vibronic coupling and pseudo-Jahn-Teller distortion.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Russell P. Hughes, Arnold L. Rheingold, Edward H. Wong, John E. Bulkowski
Summary: This research reports the synthesis and crystal structures of mer- and fac-isomers of [Cu(18N6)]2+(X )2 and compares them to a previously reported example. It is found that different crystallization conditions can lead to the formation of different isomers. The study also provides insights into the mechanistic pathway of isomer interconversion.
Article
Chemistry, Inorganic & Nuclear
Sudipta Mondal, Brigitte Schwederski, Stanislav Zalis, Wolfgang Kaim
Summary: This study synthesized asymmetrical and symmetrical dinuclear complexes and characterized their structures. The compounds showed reversible one-electron reduction and oxidation, and exhibited significant inter-valence charge transfer character.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Haolv Hu, Hung-Chieh He, Rue-Kun Xie, Chen Cheng, Tianran Yan, Chi Chen, Dan Sun, Ting-Shan Chan, Jinpeng Wu, Liang Zhang
Summary: In this study, we successfully introduced reversible Mn2+/Mn4+ double redox couple into P2-type Na0.6Mg0.3Mn0.7O2 cathode with suppressed Jahn-Teller (J-T) effect through F anion doping strategy. The introduction of F anions enlarged the interlayer spacing, reduced the band gap, improved charge transfer kinetics, suppressed Mn2+ dissolution, promoted reversible conversion, enhanced oxygen redox reaction, and ultimately enhanced the electrochemical performance.
Article
Chemistry, Inorganic & Nuclear
Alvaro Seijas-Da Silva, Jose Alberto Carrasco, Bruno J. C. Vieira, Joao C. Waerenborgh, Eugenio Coronado, Gonzalo Abellan
Summary: In this study, a hybrid NiFe-LDH family is synthesized through anion exchange reactions using surfactant molecules, increasing the interlayer space and achieving complete magnetic decoupling of the layers. The results of magnetic analysis and Mossbauer spectroscopy validate the potential of molecular engineering for designing hybrid layered magnetic materials approaching the 2D magnetic limit.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Victor Garcia-Lopez, Hanane El Mansour El Jastimi, Jana Jurakova, Miguel Clemente-Leon, Eugenio Coronado
Summary: In this study, three solvatomorphs of a two-nucleus iron(II) complex were synthesized and characterized. These solvatomorphs exhibited interesting spin crossover properties and could retain their crystallinity while allowing for the entrance or removal of solvent molecules through vapor diffusion. The spin crossover properties of the complex could be reversibly tuned by exposure to different solvents.
CRYSTAL GROWTH & DESIGN
(2023)
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
Physics, Multidisciplinary
Mattias Matthiesen, Jorrit R. Hortensius, Samuel Manas-Valero, Itzik Kapon, Dumitru Dumcenco, Enrico Giannini, Makars Siskin, Boris A. Ivanov, Herre S. J. van der Zant, Eugenio Coronado, Alexey B. Kuzmenko, Dmytro Afanasiev, Andrea D. Caviglia
Summary: The research focuses on investigating optical methods for generating coherent magnons in antiferromagnetic insulators. It is found that orbital transitions are key targets for magnetic control in insulators with zero orbital angular momentum.
PHYSICAL REVIEW LETTERS
(2023)
Article
Materials Science, Multidisciplinary
Jan N. Kirchhof, Yuefeng Yu, Denis Yagodkin, Nele Stetzuhn, Daniel B. de Araujo, Kostas Kanellopulos, Samuel Manas-Valero, Eugenio Coronado, Herre van der Zant, Stephanie Reich, Silvan Schmid, Kirill Bolotin
Summary: Nanomechanical spectroscopy (NMS) is a new approach to determine optical absorption spectra of nanoscale materials via mechanical measurements. It directly measures absorption by measuring changes in the resonance frequency of a membrane resonator. In this study, a protocol for NMS of 2D materials is developed, which improves sensitivity and simplifies the experiment. The use of low-stress silicon nitride membranes as the substrate reduces noise-equivalent power.
Article
Chemistry, Multidisciplinary
Francisco Marques-Moros, Carla Boix-Constant, Samuel Manas-Valero, Josep Canet-Ferrer, Eugenio Coronado
Summary: We conducted a comprehensive optical characterization of the van der Waals semiconductor metamagnet CrSBr using temperature- and magnetic-field-dependent photoluminescence. We observed a characteristic peak that disappeared when switching the ferromagnetic layers and exhibited a different temperature dependence from excitonic peaks. This peak's contribution to photoluminescence was enhanced around 30-40 K, coinciding with the hidden order magnetic transition temperature. Our findings reveal the connection between optical and magnetic properties through the ionization of magnetic donor vacancies and demonstrate the potential of designing 2D heterostructures with magnetic and excitonic properties.
Article
Chemistry, Multidisciplinary
Maurits J. A. Houmes, Samuel Manas-Valero, Alvaro Bermejillo-Seco, Eugenio Coronado, Peter G. Steeneken, Herre S. J. van der Zant
Summary: This article investigates the structural anisotropy of CrPS4 and its relationship with magnetic phase transitions and discovers different mechanical response behavior compared to previously studied van der Waals magnets. The results demonstrate the potential of CrPS4 in the field of low-dimensional magnetism and show the potential of mechanical resonators in studying structural modifications in 2D materials and van der Waals heterostructures.
ADVANCED FUNCTIONAL MATERIALS
(2023)
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)
Article
Chemistry, Multidisciplinary
Yishay Zur, Avia Noah, Carla Boix-Constant, Samuel Manas-Valero, Nofar Fridman, Ricardo Rama-Eiroa, Martin E. Huber, Elton J. G. Santos, Eugenio Coronado, Yonathan Anahory
Summary: This work demonstrates direct magnetic imaging of CrSBr flakes using nano-SQUID-on-tip (SOT) microscopy. It is found that the ferromagnetic order and the antiferromagnetic coupling are preserved down to the monolayer. Additionally, spin reorientation and the formation of Neel magnetic domain walls are observed even in the single-layer limit. This highlights the remarkable stability of CrSBr in the 2D limit.
ADVANCED MATERIALS
(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, Multidisciplinary
Gabriele Baglioni, Makars Siskins, Maurits Houmes, Martin Lee, Dong Hoon Shin, Samuel Manas-Valero, Eugenio M. Coronado, Yaroslav Blanter, Herre S. J. G. van der Zant, Peter Steeneken
Summary: Magnetostrictive coupling has become a sensitive method for studying magnetism in 2D materials by mechanical means. In this study, we optothermally modulate the magnetization in antiferromagnetic 2D material membranes to induce a high-frequency magnetostrictive driving force. The thermo-magnetostrictive effect near the critical temperature of magnetostrictive 2D materials provides a route for more efficient actuation of nano-magnetomechanical devices and studying the coupling among magnetic, mechanical, and thermodynamic degrees of freedom.
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, Physical
Miguel Gavara-Edo, Francisco Javier Valverde-Munoz, M. Carmen Munoz, Safaa Elidrissi Moubtassim, Francisco Marques-Moros, Javier Herrero-Martin, Kateryna Znovjyak, Maksym Seredyuk, Jose Antonio Real, Eugenio Coronado
Summary: Materials based on spin crossover molecules have attracted significant attention in molecular magnetism. This study presents a novel spin crossover material that can form thermally stable thin films while retaining its molecular bistability.
CHEMISTRY OF MATERIALS
(2023)