Article
Chemistry, Physical
Alberto Fernandez-Alarcon, Jochen Autschbach
Summary: This paper presents a conceptual review of a frequently used localized molecular orbital (LMO) analysis method for interpreting NMR parameters in compounds containing elements from across the periodic table. An example focusing on N-15 shielding in a heavy metal complex is presented.
Article
Physics, Fluids & Plasmas
Y. Ferro, E. A. Hodille, J. Denis, Z. A. Piazza, M. Ajmalghan
Summary: In this study, the adsorption of oxygen and the co-adsorption of oxygen and hydrogen on the (110) surface of tungsten were investigated using Density Functional calculations. The mechanisms of absorption, recombination and release of hydrogen on the (110) surface with oxygen were established. It was found that both hydrogen and oxygen preferentially adsorb at three-fold sites and the saturation limit for adsorbate was determined to be one monolayer. Oxygen was found to decrease the binding energy of hydrogen on the surface and lower the activation barrier for molecular hydrogen recombination. Furthermore, oversaturation of adsorbate was shown to decrease the activation barriers for both hydrogen absorption and molecular hydrogen recombination on the (110) surface of tungsten.
Article
Spectroscopy
Xie Yu-yu, Hou Xue-ling, Chen Zhi-hui, Aisa Haji Akber
Summary: With the continuous development of science and technology, new techniques have emerged in the quality control and evaluation of Traditional Chinese Medicines (TCMs). This study focuses on the molecular parameters of salidroside, a main component of Rhodiola Rosea, and provides important references for further exploration of its chemical properties and reaction mechanisms. The findings have implications for understanding the structural modification and identification of active sites.
SPECTROSCOPY AND SPECTRAL ANALYSIS
(2022)
Review
Materials Science, Coatings & Films
Raymond T. Tung
Summary: For many decades, the mystery surrounding the formation mechanism of the Schottky barrier height (SBH) was dominated by the concept of Fermi-level pinning (FLP). However, experimental research on polycrystalline metal-semiconductor interfaces revealed insensitivity of the SBH to metal work function, leading to a shift in understanding and the proposal of new theories.
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A
(2021)
Article
Physics, Condensed Matter
Katsuhiko Higuchi, Naoki Matsumoto, Yuki Kamijo, Masahiko Higuchi
Summary: The study proposes a calculation scheme for superconductors using current-density functional theory, where the attractive interaction and superconducting gap are treated as variables. By applying the scheme to simple models for aluminum, tin, and indium in a magnetic field, the magnetic field and temperature dependences of the superconducting gap are well reproduced. Additionally, it is observed that the attractive interaction changes with the magnetic field and temperature, consistent with the change in the superconducting gap.
JOURNAL OF PHYSICS-CONDENSED MATTER
(2021)
Article
Chemistry, Inorganic & Nuclear
Tony Ho-Ching Fung, Maggie Ng, Nathan Man-Wai Wu, Vivian Wing-Wah Yam
Summary: A series of cyclometalated platinum(II) complexes with a dithienylethene-containing N^C and an ancillary O^O ligand have been synthesized and characterized. These complexes exhibit photochromism that can be triggered by photoexcitation and their photophysical and photochromic properties can be tuned by varying the ligands. Moreover, the complexes demonstrate fatigue resistance and thermal irreversibility, making them promising candidates for various applications.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Physics, Multidisciplinary
Tomasz Maciazek
Summary: The reduced density matrix functional theory is a powerful tool for studying properties of ground states of strongly interacting quantum many body systems, especially Bose-Einstein condensation and systems of strongly correlated electrons. It has been shown that the density functional in these systems exhibits a repulsive gradient, known as the Bose-Einstein condensation force, which is universal for different types of pair-interaction and non-homogeneous gases. The theory has also been extended to fermionic systems, showing the existence of a similar repulsive gradient in the fermionic RDMFT.
NEW JOURNAL OF PHYSICS
(2021)
Article
Chemistry, Physical
Kailai Lin, Patrick TomHon, Soren Lehmkuhl, Raul Laasner, Thomas Theis, Volker Blum
Summary: This study provides an in-depth theoretical analysis of key chemical equilibria in Signal Amplification by Reversible Exchange (SABRE) using density functional theory calculations and harmonic transition state theory. The research shows that under typical experimental conditions, the Gibbs free energies of the two key states involved in pyridine-hydrogen exchange are essentially the same, indicating optimality for SABRE. Additionally, a methanol-containing intermediate is proposed as a plausible transient species in the process.
Article
Chemistry, Physical
Yu-Feng Ding, Shuang-Feng Yin, Meng-Qiu Cai
Summary: This study investigates the mechanisms of photocatalytic toluene selective oxidation reactions, as well as the influence of water on these reactions. The results show that the oxidation potential of the photocatalyst is crucial for efficient catalysis, and the dehydration reaction is the rate-determining step for converting toluene into benzaldehyde. Furthermore, water has a dual role in photocatalytic reactions.
Article
Materials Science, Multidisciplinary
Radek Jesko, Ondrej Stejskal, Robin Silber, Lukas Beran, Martin Veis, Ahmad Omar, Jaroslav Hamrle
Summary: The study analyzed the optical and magneto-optical properties of the Heusler compound Co2FeAl0.5Si0.5, showing that the spectral permittivity is mainly influenced by absorption by minority electrons. The best agreement between experimental and theoretical results was found for the local density approximation potential, with the half-metallic ferromagnetic character preserved only in calculations using the Coulomb interaction correction.
Article
Physics, Multidisciplinary
Mohammed Alghadeer, Abdulaziz Al-Aswad, Fahhad H. Alharbi
Summary: A highly accurate predictive model was developed using Machine Learning to estimate one-dimensional kinetic energy density functionals, showing better accuracy than standard KEDF. The statistical training approach suggested the reliability of the model for large-scale orbital free density functional theory calculations.
Article
Physics, Condensed Matter
Bao-Feng Shan, Jie Deng, Zong-Yan Zhao
Summary: Constructing CuS/Bi2S3 heterostructure can improve photocatalytic performance by promoting effective separation of photogenerated electron-hole pairs and suppressing their recombination. The interface properties of this heterostructure play a crucial role in enhancing the photocatalytic efficiency.
PHYSICA STATUS SOLIDI B-BASIC SOLID STATE PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Tanay Debnath, Kaushik Sen, A. Suresh, Pratik Swarup Dash, Abhijit K. Das
Summary: This study computationally explores the CO2 gasification process on different active edges of a specific coke model surface. It is found that the adsorption through carbon and oxygen ends of CO2 is favored, forming four- and five-membered rings on the active sites. The strength of adsorption depends on the nature and position of the active sites. The most stable intermediate is identified as having oxygen attached to the middle carbon of the coke. The energy barrier for the second CO release is also influenced by the attachment sites of oxygen on the coke surface. This work provides a more comprehensive understanding of CO2 gasification reactions by considering all active sites in a single coke model.
Article
Chemistry, Physical
Ningjing Luo, Zhufeng Hou, Guo-Liang Chai
Summary: This study systematically explores the catalytic activity of tungsten monocarbide (WC) by studying the methane dehydrogenation and C-C coupling processes on WC surfaces using density functional theory (DFT) calculations. The results indicate that the W-terminated WC(0001) surface is the most favorable exposed surface with a lower surface energy. Additionally, the Co(111), Ni(111), and W-terminated WC(0001) surfaces exhibit similar catalytic properties in methane dehydrogenation, and the rate-limiting step on the W-terminated WC(0001) surface is the dissociation of CH*. C-C coupling through CH* intermediates on the W-terminated WC(0001) surface favors the formation of C2H2 kinetically.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Physical
Cody R. Aldaz, Theodore E. Wiley, Nicholas A. Miller, Nawodi Abeyrathna, Yi Liao, Paul M. Zimmerman, Roseanne J. Sension
Summary: UV-visible transient absorption spectroscopy and quantum mechanical simulations were used to study the photochemical mechanism of two metastable merocyanine/spiropyran photoacids, revealing that isomerization leads to deprotonation and confirming that cis-phenylhydroxy-MCH is a stronger acid than trans-phenylhydroxy-MCH based on previous studies. Further investigation is needed to accurately evaluate the physical basis for the acidity of the cis photoacids.
JOURNAL OF PHYSICAL CHEMISTRY B
(2021)
Article
Chemistry, Physical
Alexandre Barrozo, Maylis Orio
Summary: The development and optimization of catalysts for H-2 production require a comprehensive understanding of the potential catalytic mechanisms involved. Transition metals are often the reactive centers in catalysis, but this can change in the presence of a redox-active ligand. Investigating the differences in catalysis when considering ligand- and metal-centered reactivity is crucial for finding the most efficient mechanisms for hydrogen evolution reaction.
Article
Chemistry, Inorganic & Nuclear
Rogelio J. Gomez-Pineiro, Maria Drosou, Sylvain Bertaina, Christophe Decroos, A. Jalila Simaan, Dimitrios A. Pantazis, Maylis Orio
Summary: This study combines experimental and computational investigations to uncover the structural identity and interpret the signals of lytic polysaccharide monooxygenases (LPMOs), copper enzymes that degrade recalcitrant polysaccharides. The findings provide a reliable spectroscopy-consistent view on the plasticity of the resting state in PlAA10 LPMO, which serves as a foundation for further elucidating structure-property relationships and the formation of catalytically competent species.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Laure de Thieulloy, Clement Barois, Cedric Mongin, Isabelle Leray, Clement Guerrin, Stephane Aloise, Guy Buntinx, Aurelie Perrier
Summary: In the context of designing efficient photocontrolled ion-release systems, a computational strategy based on charge transfer parameters is proposed to predict cation photorelease, with a success rate of approximately 80% demonstrated in experimental tests.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Maria Drosou, Christiana A. Mitsopoulou, Maylis Orio, Dimitrios A. Pantazis
Summary: Computational electron paramagnetic resonance (EPR) spectroscopy plays an important role in connecting spectroscopic observations with the fundamental description of electronic structure. This study focuses on Cu(II) complexes and investigates the performance of double-hybrid density functionals (DHDFs) for predicting g-tensors. The results show that current DHDFs consistently outperform other computational approaches, with B2GP-PLYP and PBE0-DH identified as the best DHDFs for predicting Cu(II) g-tensors.
Editorial Material
Chemistry, Multidisciplinary
Lubomir Rulisek, Maja Gruden, Maylis Orio, Robert J. Deeth
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Stefani Gamboa-Ramirez, Bruno Faure, Marius Reglier, A. Jalila Simaan, Maylis Orio
Summary: The stereoselective copper-mediated hydroxylation of intramolecular C-H bonds from tridentate ligands was reinvestigated using DFT calculations. The computational study provides a rational explanation for the observed regio- and stereoselectivity, as well as insights into the key intermediates and processes involved. These findings are important for a deeper understanding and optimization of such reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Aspasia Stoumpidi, Adelais Trapali, Marie Poisson, Alexandre Barrozo, Sylvain Bertaina, Maylis Orio, Georgios Charalambidis, Athanassios G. Coutsolelos
Summary: Iron porphyrins are efficient molecular catalysts for CO2 reduction, and a suitably modified Fe-III porphyrin showed excellent catalytic activity in the photocatalytic reduction of CO2, producing mainly CO with high selectivity.
Article
Materials Science, Multidisciplinary
Loic Soriano, Maylis Orio, Olivier Pilone, Olivier Jeannin, Eric Reinheimer, Nicolas Quemere, Pascale Auban-Senzier, Marc Fourmigue, Sylvain Bertaina
Summary: In this study, the electrocrystallization of o-DMTTF in the presence of NO2- anion resulted in the formation of (o-DMTTF)(2)NO2, which is the first example of an isolated cation radical salt with NO2-. The salt exhibited semiconducting behavior and a strong 1D structure due to the dimerization of o-DMTTF molecules. Additionally, a spin-Peierls transition was observed at 70 K. The importance of this research is rated 8 out of 10.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Medicinal
Joao V. S. Guerra, Luiz F. G. Alves, Didier Bourissou, Paulo S. Lopes-de-Oliveira, Gyorgy Szaloki
Summary: Confining molecular guests within artificial hosts has greatly contributed to the rational design of supramolecular cages. In the past 30 years, various design strategies have been developed for the controlled synthesis of diverse cages. Recently, there has been an increasing interest in utilizing in silico methods in this toolbox. Cavity characterization software, like KVFinder project and Fpocket, have shown potential in the rational design of supramolecular cages.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Article
Biochemistry & Molecular Biology
Mary-Ambre Carvalho, Khalissa Merahi, Julien Haumesser, Ana Mafalda Vaz Martins Pereira, Nathalie Parizel, Jean Weiss, Maylis Orio, Vincent Maurel, Laurent Ruhlmann, Sylvie Choua, Romain Ruppert
Summary: A series of nickel(II) porphyrins with bulky nitrogen donors were synthesized via Ullmann methodology or Buchwald-Hartwig amination reactions. X-ray structures of some compounds were determined and the electrochemical behavior was analyzed. Spectroelectrochemical measurements were used to study the electron exchange process, and electron paramagnetic resonance (EPR) and electron nuclear double resonance spectroscopy (ENDOR) were employed to determine the delocalization of radical cations and the coupling constants, respectively. DFT calculations were performed to support the EPR data.
Article
Biochemistry & Molecular Biology
Aleksandra Rancic, Nikola Babic, Maylis Orio, Fabienne Peyrot
Summary: This study investigates the stability of three newly synthesized nitroxide candidates with tetraethyl substitution and compares their stability in vivo. The results show that nitroxides with pyrrolidine and pyrroline cores exhibit higher stability compared to isoindoline nitroxide. Metabolite analysis suggests that the transformation pathway of tetraethyl isoindoline nitroxide involves hydrogen abstraction and subsequent modifications by cytochrome P450.
Article
Chemistry, Inorganic & Nuclear
Michael Papadakis, Alexandre Barrozo, Lea Delmotte, Tatiana Straistari, Sergiu Shova, Marius Reglier, Vera Krewald, Sylvain Bertaina, Renaud Hardre, Maylis Orio
Summary: Thiocarbohydrazone-based catalysts with potentially electrochemically active ligands can be easily tailored for optimization. In this study, a trinuclear nickel-thiocarbohydrazone complex is synthesized and characterized, showing an improved turnover rate compared to its mononuclear counterpart. DFT calculations reveal that the mechanism involved is metal-centered, unlike the metal-assisted ligand-centered mechanism in the mononuclear complex. Two possible mechanisms involving an initial double reduction of the system are proposed for this catalyst.
Article
Chemistry, Organic
Maksym Dekhtiarenko, Gyoergy Szaloki, Vincent Croue, Jennifer Bou Zeid, David Canevet, Magali Allain, Vincent Carre, Frederic Aubriet, Zoia Voitenko, Marc Salle, Sebastien Goeb
Summary: M4L2 metalla-cages with large electron-rich ovoid cavities were constructed through coordination-driven self-assembly from square planar palladium complexes and extended tetrathiafulvalene-based ligands. The binding properties of these cages for polyaromatic hydrocarbons (PAHs) or zinc tetraphenylporphyrin were evaluated and compared with smaller cage analogues, showing a high size selectivity.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Gyorgy Szaloki, Julien Babinot, Vlad Martin-Diaconescu, Sonia Mallet-Ladeira, Yago Garcia-Rodeja, Karinne Miqueu, Didier Bourissou
Summary: Chelating P<^>P and hemilabile P<^>N ligands were found to oxidize Au(i) complexes by o-benzoquinones. The resulting Au(iii) catecholate complexes were characterized and the reversibility of the transformation was confirmed. DFT calculations provided insights into the structure and stability of the Au(i) o-quinone and Au(iii) catecholate forms.
Article
Chemistry, Multidisciplinary
Gyorgy Szaloki, Karinne Miqueu, Didier Bourissou
Summary: Silver(I) salts can mimic copper(I) salts but not gold(I) salts in their reaction with peri-iodo naphthyldiisopropylphosphine, leading to the formation of peri-cyclic phosphonium derivatives. This represents the first example of silver-mediated P-C coupling through a two-electron redox sequence.
MENDELEEV COMMUNICATIONS
(2022)