Article
Chemistry, Physical
Jing Yang, Stefano Falletta, Alfredo Pasquarello
Summary: In this study, the accuracy of range-separated hybrid functionals in predicting band gaps of semiconducting and insulating materials is systematically evaluated and compared with their global counterparts. It is observed that range-separated hybrid functionals that accurately describe long-range dielectric screening significantly outperform standard hybrid functionals such as PBE0 and HSE06. The choice of short-range Fock exchange fraction and screening length can further reduce the prediction error. A universal expression for selecting the inverse screening parameter is proposed, resulting in a mean absolute error as small as 0.15 eV for band gap prediction.
NPJ COMPUTATIONAL MATERIALS
(2023)
Article
Chemistry, Physical
Pier Paolo Poier, Theo Jaffrelot Inizan, Olivier Adjoua, Louis Lagardere, Jean-Philip Piquemal
Summary: Using a deep neuronal network (DNN) model trained on a large data set, researchers propose a transferable density-free many-body dispersion (DNN-MBD) model. The DNN-MBD model bypasses explicit density partitioning and achieves comparable accuracy to other approaches. It reduces computational cost and can be coupled with other models for large-scale calculations.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Viki Kumar Prasad, Alberto Otero-de-la-Roza, Gino A. DiLabio
Summary: In this study, a new low-cost quantum mechanical method using atom-centered potentials (ACPs) was developed to model large molecular systems. Machine learning regression technique was utilized to train and validate the ACP-corrected methods. The proposed ACP-corrected methods showed comparable performance to complete basis set density functional theory at a much lower cost, and could improve the description of covalent and noncovalent bond geometries.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Crystallography
Anna K. Przybyl, Anita M. Grzeskiewicz, Maciej Kubicki
Summary: Eight new cytisines were synthesized and characterized, with two compounds having their X-ray crystal structures obtained for in-depth analysis of interactions and energies. The results suggest no direct connection between geometric interactions and molecule-to-molecule energies. Transfer of multipolar parameters in estimating critical points' characteristics has been confirmed to be useful.
Article
Chemistry, Physical
Enrique M. Cabaleiro-Lago, Berta Fernandez, Roberto Rodriguez-Fernandez, Jesus Rodriguez-Otero, Saulo A. Vazquez
Summary: Analytical corrections were developed to improve the accuracy of the PM6 and GFN2-xTB semiempirical quantum mechanical methods for evaluating noncovalent interaction energies in alkanes and alkenes. The approach of functional group corrections was used, where the atom-atom pair corrections depend on the nature of the interacting functional groups. The results showed that the errors obtained with the PM6-FGC and xTB-FGC methods for the included systems were within the chemical accuracy.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Geosciences, Multidisciplinary
Rong Wang, Yanrong Li, Dongdong Lv, Weichao Zhao, Chaobo Zhang, Hauke Zachert, Gerald Eichhoff, Mary Antonette Beroya-Eitner
Summary: Tensile strength is a key factor in the cracking and failure of soil or rock mass. New test methods like IHFT and HCT have advantages over traditional methods like UDTT, BT, and TPBT when it comes to testing soil and weak rocks, as they can overcome eccentric force issues and produce reproducible and stable results. HCT is found to be more suitable for routine laboratory testing due to its simpler procedure, stable results, and uniform stress distribution within specimens.
FRONTIERS IN EARTH SCIENCE
(2022)
Article
Chemistry, Physical
Pilankatta K. Ramya, Cherumuttathu H. Suresh
Summary: The structure and energetics of the interactive behavior of Li+ and Li with polycyclic aromatic hydrocarbons (PAHs) were studied. The analysis of the electron distribution in the PAHs led to the categorization of their aromatic rings into five types, and the sextet-type Rs and naphthalene-type Rn rings showed the highest interaction with Li+. The change in the distribution of the electron density at the nucleus of Li+ due to complex formation gave a quantitative measure of the electronic effect of the cation-pi binding. Carbon nanoflake-type systems, including coronene, circumbiphenyl, C42H16, and C50H18, were suggested as good anode materials for lithium ion batteries based on the cell potential prediction.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Hiram Perez, Alejandro Di Santo, Oscar E. Piro, Gustavo A. Echeverria, A. Cano, M. Gonzalez, J. Rodriguez-Hernandez, A. Ben Altabef, Antonio Frontera, Diego M. Gil
Summary: Five new transition metal nitroprussides with 1-methylimidazole have been synthesized and characterized. The complexes are 2D coordination polymers and their supramolecular self-assembly is governed by non-classical bonding interactions.
Article
Chemistry, Physical
Wenna Ai, Wei-Hai Fang, Neil Qiang Su
Summary: The short-range corrected reduced density matrix functional omega P22 is developed to utilize the advantages of functionals in KS-DFT and RDMFT without double-counting, outperforming other 1-RDM functionals in tests of thermochemistry, nonbonded interactions, and bond dissociation energy. Omega P22 shows less systematic error for systems involving fractional spins and can accurately predict the energies for different single and multiple bonds, filling a gap left by commonly used KS-DFT and RDMFT functionals.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Yi Xie, Daniel G. A. Smith, C. David Sherrill
Summary: This study presents an implementation of a symmetry-adapted perturbation theory algorithm based on density functional theory, utilizing density-fitting treatment of hybrid exchange-correlation kernels for describing monomers with hybrid functionals. The algorithm shows improved numerical stability and computational efficiency, performing well for systems with up to 3000 basis functions.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Thomas Schraivogel, Evelin Martine Christlmaier, Pablo Lopez Rios, Ali Alavi, Daniel Kats
Summary: In this study, we demonstrate the accuracy of ground-state energies of the transcorrelated Hamiltonian using sophisticated Jastrow factors obtained from variational Monte Carlo and coupled cluster methods. Our results show that the transcorrelated distinguishable cluster method can approach the complete basis limit and near full configuration interaction quality values for over thirty atoms and molecules, even with the cc-pVTZ basis. We also investigate the breaking of the nitrogen molecule with transcorrelated coupled cluster methods to assess performance in different correlation regimes.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Camilo Zuluaga, Vincent A. Spata, Spiridoula Matsika
Summary: This study compares how 40 different quantum mechanical methods describe the excited states of a guanine-thymine pi-stacked nucleobase dimer system, including both the 5'-TG-3' and 5'-GT-3' conformations. The distance between the nucleobases is found to be a major factor in determining the energy of the CT state and the difference in dipole moments between the CT and ground state. Compared to states localized on one nucleobase, there is a wider range of values (and errors) for the energies of CT states.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
Andres I. Bertoni, Cristian G. Sanchez
Summary: In this study, a chemically-informed data-driven approach was proposed to benchmark the approximate density-functional tight-binding (DFTB) excited state (ES) methods within the DFTB+ suite. Valuable insights regarding the limitations of the benchmarked methods in terms of the approximations made to density-functional theory (DFT) were extracted from the large volume of low-detail ES-data in the machine learning (ML) dataset, QM8, along with recommendations on how to overcome them. The prediction errors of the first singlet-singlet vertical excitation energies (E-1) by the DFTB-approximate methods were compared with those of less approximate methods from the reference ML-dataset, showing clear trends in the dependence on chemical identity with respect to the second-order approximate coupled cluster (CC2).
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Engineering, Marine
Jie Guo, Mi Zhao, Piguang Wang, Nan Zhang
Summary: The study compared three simplified methods for assessing hydraulic forces on structures in water, finding that accuracy may be higher when added mass depends on more structural parameters, and assuming the structure to be rigid is an effective way to simplify the analytical hydrodynamics.
Article
Chemistry, Physical
J. C. Sancho-Garcia, E. Bremond, G. Ricci, A. J. Perez-Jimenez, Y. Olivier, C. Adamo
Summary: In this study, the energy difference between the lowest singlet and triplet excited states of a set of azaphenalene compounds, which violate Hund's rule and show an inversion of state order, is calculated using a family of double-hybrid density functionals. The results demonstrate that these double-hybrid density functional models, with the approximate inclusion of double excitations, can accurately predict the energy order and energy difference of the excited states.
JOURNAL OF CHEMICAL PHYSICS
(2022)
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)