Review
Chemistry, Inorganic & Nuclear
Dumitru-Claudiu Sergentu, Jochen Autschbach
Summary: This article introduces the application of XANES spectroscopy in elucidating the metal-ligand bonding in f-element complexes and presents the corresponding calculation methods. By calculating the wavefunctions of the ground state and the excited state and considering spin-orbit effects, chemists can apply chemical bonding tools to explain the observed intensities and understand the covalent bonding.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Robert Polly, Bianca Schacherl, Joerg Rothe, Tonya Vitova
Summary: Relativistic multiconfigurational all-electron ab initio calculations, including spin-orbit interaction, accurately reproduce experimental results for uranyl's 3d4f resonant 5f inelastic X-ray scattering (RIXS) map. The calculated data provide insights into the fine structure splitting of 4f orbitals induced by trans di-oxo bonds in uranyl, allowing for a clear understanding of energy differences between 5f and 4f orbitals. Ab initio calculations show the versatility of multiconfigurational protocols in studying RIXS maps of systems containing actinides.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yangyu Zhou, Sudip Pan, Xuelin Dong, Lina Wang, Mingfei Zhou, Gernot Frenking
Summary: The study reveals that the CaCO2 complex has a specific structural feature with a significant electrostatic interaction and covalent bonds between the Ca+ cation and CO2- anion. Furthermore, the results support the assignment of heavier alkaline-earth atoms as transition metals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Materials Science, Multidisciplinary
Qing Jiang, Yi Han, Ya Zou, Chunyan Chi
Summary: Here, we report the synthesis and redox properties of two new quinodimethane-embedded expanded [11]- and [13]helicenes. These helicenes exhibit unique electronic properties with small energy gaps and amphoteric redox behavior. Furthermore, their dications and dianions show significant open-shell singlet diradical character with small singlet-triplet energy gaps.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Physics, Multidisciplinary
Quan-Wei Nan, Chao Wang, Xin-Yue Yu, Xi Zhao, Yongjun Cheng, Maomao Gong, Xiao-Jing Liu, Victor Kimberg, Song-Bin Zhang
Summary: The study presents theoretical simulations comparing XPS and RAS spectra using ultrashort x-ray pulses, revealing that resonant x-ray photoemission can achieve higher spectral resolution than conventional x-ray photoelectron spectroscopy, even in the sub-femtosecond regime. These findings suggest a new perspective for utilizing attosecond x-ray pulses in tracking electronic and molecular dynamics.
CHINESE PHYSICS LETTERS
(2023)
Article
Chemistry, Physical
Jan Thogersen, Veronica Vaida, Mikkel Bregnhoj, Tobias Weidner, Frank Jensen
Summary: The primary photolysis dynamics of aqueous lactate induced at lambda = 200 nm were studied in this research. The study showed that decarboxylation dominates the photolysis process, while dehydroxylation is not significant. The primary products of photo-dissociation are CO2 and CH3CHOH-, with CO2- being observed as a minor photo-product during the process.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Kazuki Inoue, Tenri Morimoto, Daisuke Yokogawa, Masanari Okuno
Summary: This study measured the Hyper-Raman spectra of benzene-h(6), benzene-d(6), and pyridine in the liquid phase using a high repetition rate picosecond laser. The sensitivity of our spectroscopic system was significantly improved, allowing the detection of previously unobserved HR bands. In addition, quantum chemical calculations were evaluated by comparing experimental and computational spectra.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Materials Science, Multidisciplinary
Chun-Yu Liu, Kari Ruotsalainen, Karl Bauer, Regis Decker, Annette Pietzsch, Alexander Foehlisch
Summary: The electronic and magnetic excitations of bulk NiO were studied using resonant inelastic x-ray scattering. The experimental results were consistent with crystal-field model calculations and explained the lower exchange parameter in the excited state through electronic effects and structural dynamics.
Article
Materials Science, Multidisciplinary
Elena Ferrari, Francesco Mezzadri, Matteo Masino
Summary: The temperature induced neutral to ionic phase transition is a rare phenomenon occurring in mixed stack charge transfer crystals. The study successfully grew TTF-FA crystals and demonstrated that it undergoes this phase transition.
Article
Optics
Fredrik O. L. Johansson, Elin Berggren, Lucas M. Cornetta, Denis Ceolin, Mattis Fondell, Hans Agren, Andreas Lindblad
Summary: This study investigates the radiationless decay of core excited Xe atoms in the region of Xe L3M4,5M4,5 Auger electron kinetic energies when the Xe is adsorbed on Cu, Ag, and Au surfaces. The distribution of decay channels is different compared to Xe in the gas phase. Charge transfer of the core excited electron occurs within tens of attoseconds in all systems near the ionization threshold, while it is substrate-dependent at lower excitation energies. The observation of a unique decay channel in Xe/Cu and Xe/Ag systems, but not in Xe/Au, is explained by variations in the ground state hybridization between Xe and the substrates.
Article
Physics, Multidisciplinary
T. Morimoto, H. Suzuki, T. Otaki, N. Sono, N. Kida, T. Miyamoto, H. Okamoto
Summary: The study found that strong vibrational excitation induced by MIR pulse can drive the conversion of ionic-to-neutral in TTF-CA compound, leading to collective intermolecular charge transfer and thus enabling electronic state conversion.
PHYSICAL REVIEW RESEARCH
(2021)
Article
Chemistry, Physical
Frederik Bader, Sebastian Riedel, Helmut Beckers, Carsten Mueller, Jean Christophe Tremblay, Beate Paulus
Summary: This paper explores the interaction between rare gas matrices and trifluoride guest anions through theoretical modeling, shedding light on the origin of observed matrix effects. The study reveals the structural variability in hosting trifluoride in neon and argon matrices, highlighting the importance of theoretical modeling to complement experimental observations.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Physical
Cameron J. Mackie, Alessandra Candian, Timothy J. Lee, Alexander G. G. M. Tielens
Summary: This study investigates the characteristics of CH stretching and out-of-plane bending modes in polycyclic aromatic hydrocarbon molecules using anharmonic density functional theory. The study also calculates the infrared emission spectrum of vibrationally excited species in interstellar space and compares the results with laboratory spectra. The findings have implications for understanding the molecular inventory of space.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Materials Science, Coatings & Films
A. C. F. Santos, O. Travnikova, N. Boudjemia, T. Marchenko, R. Guillemin, I. Ismail, D. Koulentianos, D. Ceolin, F. Gel'mukhanov, M. Simon, M. N. Piancastelli, R. Puettner
Summary: This study presents a resonant Auger electron spectroscopic investigation of the symmetry-forbidden 1a1g -> 6a1g excitation below the S K-shell threshold of SF6. By measuring the partial electron yield and resonant KLL Auger spectra, the researchers obtained information about the nuclear dynamics in SF6 on the femtosecond timescale.
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A
(2022)
Article
Multidisciplinary Sciences
Yanran Shang, Ying Guo, Jun Tang
Summary: The chemical composition and influencing factors of the color of iron-bearing beryl in various shades of yellow to light blue were studied. It was found that the iron content and specific absorption bands are the main factors affecting the color. The yellow tone has a greater influence on the chroma, while the blue tone has a greater influence on the hue. With increasing iron content, the lightness of the beryl decreases and the chroma increases.
SCIENTIFIC REPORTS
(2022)
Article
Chemistry, Multidisciplinary
Tarcius N. Ramos, Benoit Champagne
Summary: The Sequential Quantum Mechanics/Molecular Mechanics scheme was used to systematically investigate the polarizability and first hyperpolarizability at the water-vacuum interface. It was found that the anisotropy of the polarizability increased, and there was an increase in the response of the first hyperpolarizability.
Article
Chemistry, Multidisciplinary
Bethany R. R. Hood, Yovan de Coene, Afonso V. V. Torre Do Vale Froes, Claire F. F. Jones, Pierre Beaujean, Vincent Liegeois, Fraser MacMillan, Benoit Champagne, Koen Clays, John Fielden
Summary: Electrochemically switched 2(nd) order non-linear optical responses have been demonstrated for the first time in polyoxometalates (POMs), with an arylimido-derivative showing a leading combination of high on/off contrast (94 %), high visible transparency, and cyclability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Abel Idrice Adjieufack, Benoit Champagne, Vincent Liegeois
Summary: Bonding evolution theory was used to elucidate the reaction mechanism of the intramolecular aza-Wittig reaction. The reaction involves the formation of a cycloadduct, decarboxylation, intramolecular [2+2] cycloaddition, and retro [2+2] cycloaddition. The rate-determining step is the formation of the cycloadduct and the reaction is exergonic, resulting in the formation of the aromatic benzothiazole.
SYNTHESIS-STUTTGART
(2023)
Editorial Material
Chemistry, Multidisciplinary
Tarcius N. Ramos, Benoit Champagne
Summary: This article investigates the interfacial selectivity of second harmonic generation at the water-vacuum interface through combining classical molecular dynamics and quantum chemistry simulations, distinguishing between bulk and interfacial contributions through calculated molecular first hyperpolarizability responses.
Article
Chemistry, Physical
Tarcius N. Ramos, Laura Le Bras, Yves L. Dory, Benoit Champagne
Summary: Targeting the use of second harmonic generation (SHG) as a bioimaging technique, the SHG first hyperpolarizabilities (beta) of assemblies of benzene-1,3,5-tricarboxamide derivatives were evaluated using density functional theory. The calculations revealed that the assemblies exhibit size-dependent SHG responses, with a maximum 18-times increase in beta HRS for B4 when going from monomer to pentamer. The presence of iodine atoms on the phenyl core enhanced the intrinsic SHG responses, and the side chains affected the relative orientation of dipole moment and first hyperpolarizability vectors.
Article
Chemistry, Physical
Andrea Bonvicini, Kayn A. Forbes, David L. Andrews, Benoit Champagne
Summary: This study presents the first computational quantum-chemistry implementation of hyper-Rayleigh scattering optical activity (HRS-OA), a nonlinear chiroptical phenomenon. The equations for simulating the differential scattering ratios of HRS-OA are derived based on the theory of quantum electrodynamics and the interactions of electric dipole, magnetic dipole, and electric quadrupole. Computation results of HRS-OA quantities for a chiral organic molecule (methyloxirane) using a broad range of atomic orbital basis sets are presented and analyzed, demonstrating the ability of HRS-OA to distinguish between enantiomers of the same chiral molecule.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Francois Mairesse, Benoit Champagne
Summary: The quantum treatment of electrons at the Kohn-Sham Density Functional Theory (DFT) level of approximation is used to optimize the structure of four organic and organo-metallic crystalline systems with nonlinear optical properties. The study addresses the lack of London-type interactions description in exchange-correlation functionals (XCFs) by employing the D* scheme, a variation of the D2 correction scaled for crystal solid state interactions. The performance and suitable scaling factors of the D* scheme are demonstrated for four representative XCFs.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2023)
Article
Chemistry, Physical
Komlanvi Sevi Kaka, Pierre Beaujean, Frederic Castet, Benoit Champagne
Summary: Recent measurements of the third harmonic scattering responses of molecules have provided new insights into computing molecular second hyperpolarizabilities (gamma) and deducing structure-property relationships. This paper evaluates the second hyperpolarizability of the pi-nitroaniline molecule using various wavefunction and density functional theory methods. The results show that the MP2 scheme offers the best accuracy/cost ratio for computing static gamma, while density functional theory methods still face challenges in accurately computing gamma. Additionally, the double-hybrid B2-PLYP functional provides accurate estimates of static gamma values.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Andrea Bonvicini, Benoit Champagne
Summary: In this work, the expressions for the third-harmonic scattering optical activity (THS-OA) spectroscopic responses are derived by combining molecular quantum electrodynamics (QED) and response theory, allowing for their computational implementation. The study shows how the pure and mixed second hyperpolarizabilities can be obtained as specific cases of a generic cubic response function, enabling the calculation of THS-OA spectroscopy.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Andrea Bonvicini, Benoit Champagne
Summary: This paper discusses the theoretical formulation and computational procedure of linear and nonlinear molecular spectroscopies applied to isotropic samples. It introduces the concept of rotational averaging of Cartesian tensors and proposes a heuristic computational method for finding linearly independent fundamental isotropic Cartesian tensors.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Carmelo Naim, Raphael Vangheluwe, Isabelle Ledoux-Rak, Benoit Champagne, Claire Tonnele, Mireille Blanchard-Desce, Eduard Matito, Frederic Castet
Summary: The second-order nonlinear optical properties of four series of amphiphilic cationic chromophores have been investigated experimentally and theoretically. The theoretical methodology combining classical molecular dynamics and quantum chemical calculations provides a rational approach for designing SHG dyes based on EFISH measurements. The good agreement between experimental and theoretical results demonstrates the usefulness of this MD + QM scheme.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Charlotte Bouquiaux, Frederic Castet, Benoit Champagne
Summary: Lipid molecules play important roles in cell functions and their structural diversity is related to different fatty acids. The nature of fatty acids has an additive effect on the overall membrane structure. Nonlinear optical responses of an embedded chromophore can be used to study the local structure of cell membranes.
Article
Chemistry, Physical
Charlotte Bouquiaux, Pierre Beaujean, Tarcius N. Ramos, Frederic Castet, Vincent Rodriguez, Benoit Champagne
Summary: The solvent effects on the optical properties of an ANEP dye were studied using experimental and theoretical methods. Experimental measurements showed a decrease in the hyperpolarizablity of the dye in polar solvents, which was confirmed by theoretical calculations using different solvation models.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Sergey Yu. Ketkov, Sheng-Yuan Tzeng, Elena A. Rychagova, Anton N. Lukoyanov, Wen-Bih Tzeng
Summary: Metallocenes, including methylcobaltocene, play important roles in various fields of chemistry. The ionization energy and vibrational structure of (Cp ')(Cp)Co can be influenced by introducing methyl substituents. The mass-analyzed threshold ionization spectrum and DFT calculations provide accurate information about the properties and transformations of (Cp ')(Cp)Co.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Review
Chemistry, Physical
Qifeng Mu, Jian Hu
Summary: Polymer mechanochemistry has experienced a renaissance due to the rapid development of mechanophores and principles governing mechanochemical transduction or material strengthening. It has not only provided fundamental guidelines for converting mechanical energy into chemical output, but also found applications in engineering and smart devices.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Da Hye Yang, Francesco Ricci, Fredrik L. Nordstrom, Na Li
Summary: Through systematic evaluation of the oiling-out behavior of procaine, we identified both stable and metastable liquid-liquid phase separation, and established phase diagrams to assist in rational selection of crystallization strategies.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Vikki Anand Varma, Simmie Jaglan, Mohd Yasir Khan, Sujin B. Babu
Summary: Designing engineering structures like nanocages, shells, and containers through self-assembly of colloids is a challenging problem. This work proposes a simple model for the subunit, which leads to the formation of monodispersed spherical cages or containers. The model with only one control parameter can be used to design cages with the desired radius.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Hainan Jiang, Yaolong He, Xiaolin Li, Zhiyao Jin, Huijie Yu, Dawei Li
Summary: The cycling lifespan and coulombic efficiency of lithium-ion batteries are crucial for high C-rate applications. The Li-ion concentration plays a crucial role in determining the mechanical integrity and structural stability of electrodes. This study focuses on graphite as the working electrode and establishes an experimental system to investigate the mechanical properties of composite graphite electrode at different C-rates. Considering the effect of Li-ion concentration in stress analysis is found to be significant.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Zhiye Wang, Yunchuan Li, Mingjun Sun
Summary: This study investigates the influence of intramolecular pi-pi interactions on the electronic transport capabilities of molecules. By designing and analyzing three pi-conjugated molecules, the researchers observe that different pi-conjugated structures have varying effects on electron transport. The findings provide a theoretical foundation for designing single-molecule electronic devices with multiple electron channels based on intramolecular pi-pi interactions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Yuandong Xu, Haoyang Feng, Chaoyang Dong, Yuqing Yang, Meng Zhou, Yajun Wei, Hui Guo, Yaqing Wei, Jishan Su, Yingying Ben, Xia Zhang
Summary: Hollow MoS2 cubes and spheres were successfully synthesized using a one-step hydrothermal method with the hard template method. The hollow MoS2 cubes exhibited higher specific capacitance and energy density compared to the hollow MoS2 spheres. The symmetrical supercapacitors assembled with these hollow structures showed good performance and high capacity retention after multiple cycles. These findings suggest that controlling the pore structure and surface characteristics of MoS2 is crucial for enhancing its electrochemical properties.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Ainhoa Oliden-Sanchez, Rebeca Sola-Llano, Joaquin Perez-Pariente, Luis Gomez-Hortiguela, Virginia Martinez-Martinez
Summary: The combination of photoactive molecules and inorganic structures is important for the development of advanced materials in optics. In this study, bulky dyes were successfully encapsulated in a zeolitic framework, resulting in emission throughout the visible spectrum.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Miaomiao Zhang, Cunyuan Pei, Qiqi Xiang, Lintao Liu, Zhongxu Dai, Huijuan Ma, Shibing Ni
Summary: The design of a solid electrolyte interphase (SEI) plays a crucial role in improving the electrochemical performance of anode materials. In this study, lithium difluoro(oxalate)borate (LiDFOB) is used as an electrolyte additive to form a protective SEI film on Li3VO4 (LVO) anodes. The addition of LiDFOB results in a dense, uniform, stable, and LiF-richer SEI, which enhances the Li-ion storage kinetics. The generated SEI also prevents further decomposition of the electrolyte and maintains the morphology of LVO anodes during charge/discharge processes. This work demonstrates the effectiveness of LiDFOB as a multi-functional additive for LiPF6 electrolytes and provides insights into SEI construction for high-performance LVO anodes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
B. V. Andryushechkin, T. V. Pavlova, V. M. Shevlyuga
Summary: The atomic structure of the Ag(111)-p(4 x 4)-O phase was reexamined and two phases with the same periodicity were discovered. It was demonstrated that the accepted Ag6 model is incompatible with high-resolution oxygen-sensitive STM images.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
S. L. Romo-Avila, D. Marquez-Ruiz, R. A. Guirado-Lopez
Summary: In this study, we used density functional theory (DFT) calculations to investigate the interaction between model graphene oxide (GO) nanostructures and chlorine monoxide ClO. We aimed to understand the role of this highly oxidizing species in breaking C-C bonds and forming significant holes on GO sheets. Our results showed that C-C bonds in a single graphene oxide sheet can be broken through a simple mechanism involving the dissociation of two chemically attached ClO molecules. The formation of carbonyl groups and holes on the GO surface was also observed. This study provides important insights into the degradation of carbon nanotubes and the stability of GO during the myeloperoxidase (MPO) catalytic cycle.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Alberto Garcia-Fernandez, Birgit Kammlander, Stefania Riva, Hakan Rensmo, Ute B. Cappel
Summary: In this study, the X-ray stability of five different lead halide perovskite compositions (MAPbI3, MAPbCl3, MAPbBr3, FAPbBr3, CsPbBr3) was investigated using photoelectron spectroscopy. Different degradation mechanisms and resistance to X-ray were observed depending on the crystal composition. Overall, perovskite compositions based on the MA+ cation were found to be less stable than those based on FA+ or Cs+. Metallic lead formation was most easily observed in the chloride perovskite, followed by bromide, and very little in MAPbI3. Multiple degradation processes were identified for the bromide compositions, including ion migration, formation of volatile and solid products, as well as metallic lead. CsBr was formed as a solid degradation product on the surface of CsPbBr3.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Timofei Rostilov, Vadim Ziborov, Alexander Dolgoborodov, Mikhail Kuskov
Summary: The shock-loading behavior of nanomaterials is investigated in this study. It is found that shock compaction waves exhibit a distinct two-step structure, with the formation of faster precursor waves that travel ahead of the main compaction waves. The complexity of the shock Hugoniot curve of the tested nanomaterial is described, and the effect of initial porosity on the compressed states is demonstrated.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Sergey S. Nikitin, Alexander D. Koryakov, Elizaveta A. Antipinskaya, Alexey A. Markov, Mikhail V. Patrakeev
Summary: The stability of La1/3Sr2/3Fe1-xMnxO3-delta, a perovskite-type oxide, under reducing conditions is dependent on the manganese content. Increasing the manganese content leads to a decrease in stability. The behavior of iron and manganese in the oxide shows distinct differences, which can be attributed to the difference in the enthalpy of oxidation reactions. Additionally, the change in the La/Sr ratio affects the concentration of iron and manganese ions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Physical
Mosayeb Naseri, Shirin Amirian, Mehrdad Faraji, Mohammad Abdur Rashid, Maicon Pierre Lourenco, Venkataraman Thangadurai, D. R. Salahub
Summary: Inspired by the successful transfer of freestanding ultrathin films of SrTiO3 and BiFeO3, this study assessed the structural stability and investigated the electronic, optical, and thermoelectric properties of a group of two-dimensional perovskite-type materials called perovskenes. The findings revealed that these materials are wide bandgap semiconductors with potential application in UV shielding. Moreover, they exhibit better electrical and thermal conductivity at high temperatures, enabling efficient power generation in thermoelectric devices.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)