Article
Geochemistry & Geophysics
Chao Wang, Lu'an Ren, Jesse B. B. Walters, Lifei Zhang, Renbiao Tao
Summary: In this study, natural siderite and rhodochrosite were characterized using Raman spectroscopy in an externally heated diamond-anvil cell. The Raman frequency shifts of both minerals were found to be related to pressure and temperature, and the effect of the P-T cross derivative term cannot be neglected. Based on the functional relationship between frequency and pressure/temperature, calibration curves were developed for both minerals. This is significant for studying water-carbonate interaction at high P-T conditions.
AMERICAN MINERALOGIST
(2023)
Article
Chemistry, Analytical
Christian Albers, Robin Sakrowski, Nicola Thiering, Lelia Libon, Georg Spiekermann, Johannes M. Kaa, Hlynur Gretarsson, Martin Sundermann, Metin Tolan, Max Wilke, Christian Sternemann
Summary: X-ray spectroscopy of iron-bearing compounds under high pressure and high temperature is a valuable tool for understanding geological processes in the deep Earth. A setup for resonant and non-resonant X-ray emission spectroscopy is presented, which allows for in situ studies at high pressure and high temperature. The results demonstrate the potential of this setup for quick and robust spin-state analysis, providing important insights into the behavior of iron in different environments.
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY
(2023)
Article
Chemistry, Multidisciplinary
Raul Diaz-Torres, Guillaume Chastanet, Eric Collet, Elzbieta Trzop, Phimphaka Harding, David J. Harding
Summary: The influence of solvent on the spin crossover behavior of two solvates [Fe(qsal-I)(2)]NO(3 center dot)2ROH (qsal-I = 4-iodo-2-[(8-quinolylimino)methyl]phenolate; R = Me 1 or Et 2) is investigated. Solvate 1 undergoes a symmetry-breaking phase transition from a [HS] to [HS-LS] state at 210 K, while the EtOH solvate shows complete spin crossover at T-1/2 = 250 K. The MeOH solvate exhibits LIESST and reverse-LIESST from the [HS-LS] state, revealing a hidden [LS] state. Photocrystallographic studies on solvate 1 reveal re-entrant photoinduced phase transitions to a high symmetry [HS] phase or a high symmetry [LS] phase under irradiation at 980 nm or 660 nm, respectively. This study presents the first example of bidirectional photoswitchability and subsequent symmetry-breaking from a [HS-LS] state in an iron(III) spin crossover material.
Article
Chemistry, Multidisciplinary
Lukas Schifferle, Sergey S. Lobanov
Summary: This study investigates the chemical bonding evolution in ferropericlase using high-pressure optical absorption spectra and published X-ray absorption spectroscopy data. The results show that the covalency of the Fe-O bond increases with pressure, but a spin transition at a specific pressure range weakens the Fe-O bond.
ACS EARTH AND SPACE CHEMISTRY
(2022)
Article
Chemistry, Physical
Ngoc Minh Tran, Marlene Palluel, Nathalie Daro, Guillaume Chastanet, Eric Freysz
Summary: In this study, the spin-state photoswitching process in Au@SCO nanohybrids made of gold nanorods is investigated, showing different dynamics under different excitation methods. It is found that the spin-state transition in the nanohybrids requires lower energy compared to SCO nanoparticles. A simple model is proposed to explain the experimental results.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Inorganic & Nuclear
Shu-Ya Zhang, Hui-Ying Sun, Run-Guo Wang, Yin-Shan Meng, Tao Liu, Yuan-Yuan Zhu
Summary: The self-assembly of multinuclear SCO complexes is appealing for the discovery of unique properties. In this work, three dinuclear cobalt(II) complexes were prepared using a complementary terpyridine ligand pair strategy. The complexes show different spin crossover behaviors and demonstrate the practicality of the complementary terpyridine ligand pairing in constructing multinuclear SCO-active compounds.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Amandine Bellec, Massine Kelai, Arthur Tauzin, Anastasia Railean, Vincent Repain, Jerome Lagoute, Yann Girard, Sylvie Rousset, Edwige Otero, Talal Mallah, Marie-Laure Boillot, Cristian Enachescu
Summary: In this study, the photoexcitation of ultrathin films of [FeII((3, 5-(CH3)2Pz)3BH)2] (Pz = pyrazolyl) adsorbed on a special substrate was investigated. The anomalous light-induced spin-state switching was observed for sub-monolayer coverage, while the well-known light-induced excited spin-state trapping effect was recovered for higher coverages. The combination of continuous light excitation and thermal cycling revealed light-induced thermal hysteresis for thicker films and extended thermal conversion over a large temperature range for sub-monolayer coverage. Mechanoelastic simulations showed opposite behaviors in different layers of the films due to intermolecular interactions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Li Sun, Mamadou Ndiaye, Nour El Islam Belmouri, Koen Robeyns, Aurelian Rotaru, Kamel Boukheddaden, Yann Garcia
Summary: This article introduces a porous 3D FeII coordination polymer made of 4,4'-bipyridine ligands and [N(CN)2]- organic bridges. The study found that it exhibits large volume porosity and temperature-sensitive magnetic behavior, with investigations into the solvent's influence on the magnetic properties.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Physical
Mamadou Ndiaye, Kamel Boukheddaden
Summary: This theoretical study investigates the effect of pressure on spin-crossover phenomena using an electro-elastic description and a Monte Carlo technique. The results demonstrate that a wide range of experimental observations, including conventional pressure effects, unconventional behaviors, re-entrant transitions, and double step transitions, can be qualitatively described by this model.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Inorganic & Nuclear
Iryna S. Kuzevanova, Olesia I. Kucheriv, Volodymyr M. Hiiuk, Dina D. Naumova, Sergiu Shova, Sergii I. Shylin, Volodymyr O. Kotsyubynsky, Aurelian Rotaru, Igor O. Fritsky, Il'ya A. Gural'skiy
Summary: This study reports the first Fe-II Hofmann clathrate analogues with unsubstituted 1,2,3-triazole, which exhibit temperature induced spin transition. The two new coordination polymers undergo abrupt hysteretic spin crossover in the range of 190-225 K, displaying a stable thermal hysteresis loop and strong thermochromic effect. The use of 1,2,3-triazole in spin-crossover Hofmann clathrate analogues can advantageously expand the family of complexes.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Vibe B. Jakobsen, Shalinee Chikara, Jie-Xiang Yu, Emiel Dobbelaar, Conor T. Kelly, Xiaxin Ding, Franziska Weickert, Elzbieta Trzop, Eric Collet, Hai-Ping Cheng, Grace G. Morgan, Vivien S. Zapf
Summary: The study reveals a giant magnetoelectric effect in a specific compound, where a permanent switching of structural, electrical, and magnetic properties can be induced by applying a magnetic field. This effect is attributed to the change in spin states leading to polarization and symmetry-breaking phase transitions.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Kishalay Bhar, Wenbin Guo, Mathieu Gonidec, Venkata Nikhil M. Raj, Surabhi Bhatt, Franc Perdih, Philippe Guionneau, Guillaume Chastanet, Anuj K. Sharma
Summary: We synthesized a series of molecular complexes with spin crossover behavior and successfully observed their structures and transition processes in crystals. Complexes 1 and 2 exhibit complete and gradual spin crossover at higher temperatures, while complex 3 shows strong irreversible features at lower temperatures.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Daniel Vidal, Jordi Cirera, Jordi Ribas-Arino
Summary: By studying a dataset of 24 different Fe(iii) hexacoordinated complexes, it was demonstrated that the B3LYP* functional is accurate in predicting spin-state energy gaps and distinguishing spin states of Fe(iii) complexes across a range of temperatures. This suggests that B3LYP* is a reliable method for screening new spin-crossover systems with tailored properties.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Inorganic & Nuclear
Bijoy Dey, Vadapalli Chandrasekhar
Summary: This review focuses on spin crossover phenomena, particularly in Fe-II complexes in the N4O2 coordination environment. It discusses three ligand families: Jager-type ligands, hydrazone-based ligands, and tridentate ligands with salicylaldehyde derivatives. It explores the assembly of mononuclear and multinuclear complexes, as well as the coupling of optical and magnetic properties.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Evridiki Michaels, Izar Capel Berdiell, Hari Babu Vasili, Christopher M. Pask, Mark J. Howard, Oscar Cespedes, Malcolm A. Halcrow
Summary: The complex salts [FeL2]X2 exhibit spin-transitions at specific temperatures, with a significant effect of thermally induced excited spin-state trapping observed in 1[ClO4]2. The crystal structure of 1[BF4]2 undergoes a phase transition at different temperatures, while the phase transition in 1[ClO4]2 remains unchanged between 100 and 300 K.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Geochemistry & Geophysics
Man Xu, Zhicheng Jing, Tony Yu, E. Ercan Alp, Barbara Lavina, James A. Van Orman, Yanbin Wang
Summary: Iron-rich silicate melts have been studied for their elastic properties, specifically sound velocities, at high pressure and temperature conditions. The results show that iron can reduce sound velocity while increasing density of silicate melts. The study also found that although density of the melts can be described by a linear mixing law empirically, sound velocities do not vary with composition linearly.
EARTH AND PLANETARY SCIENCE LETTERS
(2022)
Article
Geochemistry & Geophysics
Claire C. Zurkowski, Barbara Lavina, Stella Chariton, Sergey Tkachev, Vitali B. Prakapenka, Andrew J. Campbell
Summary: The phase stability of Fe2S in the Fe-S system was studied using a laser-heated diamond-anvil cell. The structure of Fe2S was determined using single-crystal X-ray diffraction techniques under high pressure and temperature conditions. This study provides the first high-pressure structural solution and refinement of Fe2S and establishes the stability of C23 Fe2S under these conditions. Previous research reported an orthorhombic Fe2S phase with a C37 structure at higher pressures and temperatures.
AMERICAN MINERALOGIST
(2022)
Article
Chemistry, Multidisciplinary
Yong-Hyun Kim, Yoo Soo Yi, Hyo-Im Kim, Paul Chow, Yuming Xiao, Guoyin Shen, Sung Keun Lee
Summary: This study reports the pressure-driven changes in the electronic configurations and their delocalization around oxygen in glasses using inelastic X-ray scattering spectroscopy. The results reveal that the densification of the glass is a result of an increase in oxygen proximity and the formation of topologically disordered oxygen configurations. The findings suggest the electronic origins of densification in heavy-metal-bearing oxide glasses and shed light on the direct probing of the electronic density of states in high-Z oxides under compression.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Seth Iwan, Chia-Min Lin, Christopher Perreault, Kallol Chakrabarty, Cheng-Chien Chen, Yogesh Vohra, Rostislav Hrubiak, Guoyin Shen, Nenad Velisavljevic
Summary: High-entropy transition metal borides offer novel opportunities for designing materials with crystalline phase stability, high strength, and thermal oxidation resistance under extreme conditions. The comprehensive theoretical and experimental investigation of prototypical high-entropy boride materials showed excellent performance in terms of compressive strength and phase stability, making them suitable for structural applications in nuclear and aerospace fields.
Article
Geochemistry & Geophysics
C. C. Zurkowski, B. Lavina, S. Chariton, V. Prakapenka, A. J. Campbell
Summary: The phase relations of Fe-FeS and the crystallization sequence of planetary cores were investigated using single crystal X-ray diffraction and laser heated diamond anvil cell. Fe2S and Fe12S7 were found to cocrystallise under high pressure and temperature conditions. These findings reveal the complex FeS phase assemblages and provide insights into the formation of iron-rich planetary cores.
GEOCHEMICAL PERSPECTIVES LETTERS
(2022)
Article
Materials Science, Multidisciplinary
Wenli Bi, Trenton Culverhouse, Zachary Nix, Weiwei Xie, Hung-Ju Tien, Tay-Rong Chang, Utpal Dutta, Jiyong Zhao, Barbara Lavina, Esen E. Alp, Dongzhou Zhang, Jingui Xu, Yuming Xiao, Yogesh K. Vohra
Summary: This study presents a comprehensive high-pressure investigation of the crystal structure and magnetic ground state of the intrinsic topological magnet EuSn2P2. The results reveal that pressure induces a phase transition in EuSn2P2 from a rhombohedral crystal structure to an amorphous phase, accompanied by an enhancement of the magnetic ordering temperature. It is also found that the pressure-induced amorphous phase leads to an intermediate valence state of the Eu ions and further increases the magnetic ordering temperature.
NPJ QUANTUM MATERIALS
(2022)
Article
Physics, Multidisciplinary
Matthew R. Diamond, Guoyin Shen, Dmitry Y. Popov, Changyong Park, Steven D. Jacobsen, Raymond Jeanloz
Summary: High-pressure single-crystal x-ray diffraction is used to experimentally map the electron-density distribution changes in (Fe,Mg)O as ferrous iron undergoes a pressure-induced transition from high- to low-spin states. Our results have applications to geophysics as well as to validating first-principles calculations, as this electronic transition affects the bulk density and elasticity of magnesiow??stite, one of the dominant mineral phases of Earth's mantle. The observed changes in diffraction intensities indicate a spin-transition-induced change in orbital occupancies of the Fe ion, in line with crystal-field theory.
PHYSICAL REVIEW LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Michal L. Chodkiewicz, Roman Gajda, Barbara Lavina, Sergey Tkachev, Vitali B. Prakapenka, Przemyslaw Dera, Krzysztof Wozniak
Summary: Water is essential for living organisms, and the structures of ice crystals have many unresolved problems. This study presents accurate crystal structures of H2O, D2O, and mixed ice VI using Hirshfeld atom refinement combined with X-ray diffraction. The results show that X-ray diffraction combined with HAR can compete with neutron diffraction in detailed studies of ice polymorphs.
Article
Geochemistry & Geophysics
Claire C. Zurkowski, Barbara Lavina, Abigail Case, Kellie Swadba, Stella Chariton, Vitali Prakapenka, Andrew J. Campbell
Summary: This study investigated the phase relations of the iron-sulfur system at high pressures and temperatures, and discovered a new hexagonal Fe5S2 sulfide. The crystallization of Fe5S2 may affect the elastic and electrical properties of Earth and planetary cores, and it may deposit in the outer third of the cores during cooling.
EARTH AND PLANETARY SCIENCE LETTERS
(2022)
Article
Chemistry, Physical
Zhou Lu, Cynthia M. Archambault, Shan Li, Umar Syed, Sicheng Wang, Abinaya Kumar, Guoyin Shen, Zhenxian Liu, Mohammad A. Omary, Hao Yan
Summary: Metallophilicity in multinuclear systems exhibits intrinsic anisotropy under isotropic compression, resulting in anomalous anisotropies in (supra)molecular structures, vibrations, and interaction energies. Mechanical pressure modulation also enhances piezochromic luminescence with similar to 103 modulation.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Geochemistry & Geophysics
Benjamin Strozewski, Johannes Buchen, Wolfgang Sturhahn, Takayuki Ishii, Itaru Ohira, Stella Chariton, Barbara Lavina, Jiyong Zhao, Thomas S. Toellner, Jennifer M. Jackson
Summary: The stability of hydrous phases in high temperature and pressure suggests that they can transport significant amounts of hydrogen into Earth's deep interior. The changes in spin state of Fe3+ in (Al, Fe)-phase H result in a decrease in bulk sound velocity, which occurs over a different pressure range compared with d-(Al, Fe)OOH. The presence of (Al, Fe)-phase H in subducted oceanic crust may contribute to seismic scattering in the mid-lower mantle and reproduce seismic signatures of large provinces.
JOURNAL OF GEOPHYSICAL RESEARCH-SOLID EARTH
(2023)
Article
Multidisciplinary Sciences
Sung Keun Lee, Yoosoo Yi, Yong-Hyun Kim, Hyo-im Kim, Paul Chow, Yuming Xiao, Peter Eng, Guoyin Shen
Summary: Diamond's unprecedented hardness is due to its electronic bonding nature under extreme pressure, which has been experimentally observed through inelastic x-ray scattering spectra measurements up to 2 million atmospheres. The observed changes in electronic structure reveal the ability of diamond to withstand deformation and internal stress, shedding light on the origin of its hardness.
Article
Chemistry, Multidisciplinary
Jin Xiong, Qing Liu, Barbara Lavina, Michael Y. Hu, Jiyong Zhao, Esen E. Alp, Liang Deng, Shengfa Ye, Yisong Guo
Summary: This study reports on rare S=1 iron(iv)-bisimido complex and its S=0 congeners. Spectroscopic and computational studies reveal that the unique electronic structure of the S=1 complex provides advantages for facile C-H activation compared to the S=0 counterparts.
Article
Chemistry, Physical
Yachao Zeng, Chenzhao Li, Boyang Li, Jiashun Liang, Michael Zachman, David Cullen, Raphael Hermann, E. Ercan Alp, Barbara Lavina, Stavros Karakalos, Marcos Lucero, Bingzhang Zhang, Maoyu Wang, Zhenxing Feng, Guofeng Wang, Jian Xie, Deborah Myers, Jean-Pol Dodelet, Gang Wu
Summary: This study reported a method of using H2 to improve the active site density of traditional Fe-N-C catalysts while stabilizing the presence of active sites, breaking the activity-stability trade-off.
Article
Physics, Multidisciplinary
B. Lavina, E. Zanardi, A. Mujica, H. Cynn, Y. Meng, J. S. Smith, M. Kong, Y. Lee
Summary: The powdered sample of gallium phosphide was compressed and heated in a laser-heated diamond anvil cell, then characterized using synchrotron x-ray diffraction. The experimental results were compared with first-principles calculations, showing close agreement. The synthesized phase exhibited variable grain sizes and a distorted tetrahedral coordination geometry, with largest grains located in the middle of the heated spot.
HIGH PRESSURE RESEARCH
(2022)