Article
Chemistry, Physical
D. Hagebaum-Reignier, J. Racine, S. Humbel
Summary: This article investigates valence bond (VB) wave functions from the perspective of density, showing that the coupling of ionic and covalent components leads to modifications in electronic density.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Medicinal
Samuel J. H. Gaughan, Jonathan D. Hirst, Anna K. Croft, Christof M. Jager
Summary: Enzyme-based iron-sulfur clusters play crucial roles in many essential biological processes, and their reactivity can be manipulated through rational engineering of oriented electric fields.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2022)
Article
Physics, Multidisciplinary
Max Nusspickel, George H. Booth
Summary: In this study, a new quantum embedding theory is proposed, which combines density-matrix embedding theory with local correlation approaches from quantum chemistry. This theory allows for systematic convergence of properties of real materials and can provide accurate results without the need for empirical parameters.
Article
Chemistry, Physical
Kai Trepte, Sebastian Schwalbe, Simon Liebing, Wanja T. Schulze, Jens Kortus, Hemanadhan Myneni, Aleksei V. Ivanov, Susi Lehtola
Summary: Fermi-Lowdin orbitals are localized orbitals commonly used with the SIC method, and they have an important role in analyzing symmetry breaking and dipole moments in chemical structures.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Optics
Caio Fernando e Silva, Alex E. Bernardini
Summary: By utilizing an information-based approach, the study examines Dirac spinors under a constant magnetic field to obtain the phase-space representation of symmetric and antisymmetric localized Dirac cat states. The research delves into the intrinsic entanglement profile implied by the Dirac Hamiltonian, shedding light on quantum states as carriers of qubits correlated by phase-space variables. Cat states, as superpositions of Gaussian states, exhibit nontrivial elementary information dynamics involving the interplay between intrinsic entanglement and quantum superposition reported by the corresponding Dirac archetypes.
Article
Chemistry, Physical
Isaac Mastalski, Nathan Sidhu, Ali Zolghadr, Saurabh Maduskar, Bryan Patel, Sundararajan Uppili, Tony Go, Ziwei Wang, Matthew Neurock, Paul J. Dauenhauer
Summary: The demand for polyolefins can be met by recycling plastic materials back to their monomers, ethylene and propylene, through thermal cracking in a pyrolysis reactor. To optimize the chemistry for maximum yield of light olefins, a detailed description of the chemical mechanisms and kinetics is required. Experimental measurements and modeling of low-density polyethylene pyrolysis kinetics demonstrate an activation energy of 225+/-16 kJ mol-1.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Carlos H. Borca, Zachary L. Glick, Derek P. Metcalf, Lori A. Burns, C. David Sherrill
Summary: The use of many-body expansion (MBE) method, combining CCSD(T)/CBS for closest dimers and trimers and MP2 for more distant ones, shows promising results in efficiently calculating lattice energies in organic crystals. The effectiveness of MP2(+ATM) as a replacement for CCSD(T)/CBS is demonstrated. The CCSD(T)/CBS best estimate of the lattice energy at 0 K is -54.01 kJ mol(-1).
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Inorganic & Nuclear
Abril C. Castro, Michele Cascella, Robin N. Perutz, Christophe Raynaud, Odile Eisenstein
Summary: In this study, a computational protocol is used to model and analyze the 19F solid-state NMR chemical shifts of a series of nickel complexes with halogen bonds. It is found that the halogen bond affects the NMR chemical shift of the nickel-bonded fluoride.
INORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Arun Ramanathan, Jensen Kaplan, Dumitru-Claudiu Sergentu, Jacob A. Branson, Mykhaylo Ozerov, Alexander I. Kolesnikov, Stefan G. Minasian, Jochen Autschbach, John W. Freeland, Zhigang Jiang, Martin Mourigal, Henry S. La Pierre
Summary: This study reveals the failure of the traditional ionic model in tetravalent praseodymium ions, as well as the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f(1) configuration with ligand valence electrons. The competition between crystal-field and spin-orbit-coupling interactions alters the spin-orbital magnetism of tetravalent praseodymium, making it resemble that of high-valent actinides.
NATURE COMMUNICATIONS
(2023)
Article
Spectroscopy
Xuan Meng, Liying Song, Haiyun Han, Jinfeng Zhao, Daoyuan Zheng
Summary: This study investigates the excited-state intramolecular proton transfer (ESIPT) mechanisms and solvent effects for three novel 3-hydroxylflavone derivatives in various solvents. It is found that the excited-state hydrogen bonds strengthen as solvent polarity decreases, which lays the foundation for designing novel solvatofluorochromic probes based on flavonoids in the future.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2022)
Article
Chemistry, Multidisciplinary
Victor Garcia, David Zorrilla, Manuel Fernandez, Jesus Sanchez-Marquez
Summary: The SBO4-DZ(d,p)-3G basis sets were modified by adding a second D shell to improve their performance in calculating the atomization energies of organic molecules. The scale factor was calculated by optimizing atomization energies directly, leading to results very similar to those of the cc-pV5Z basis sets. Optimal SBO basis sets for HF, DFTs, and MP2 were obtained by optimizing simplified box orbital (SBO) basis sets for different methods.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2021)
Article
Chemistry, Physical
Bruno Senjean, Souloke Sen, Michal Repisky, Gerald Knizia, Lucas Visscher
Summary: Localization of molecular orbitals is important in representing chemical bonding and in local correlation treatments beyond mean-field approximation. This paper generalizes intrinsic atomic and bonding orbitals to relativistic applications using complex and quaternion spinors, as well as incorporating molecular fragments. By performing a singular value decomposition, the method shows how localized valence virtual orbitals can be expressed on an intrinsic minimal basis. The developed scheme is implemented into a standalone program interfaced with various quantum chemistry packages, demonstrating its applicability on systems of increasing complexity.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Materials Science, Multidisciplinary
Shuo Wang, Yujing Wu, Hong Li, Liquan Chen, Fan Wu
Summary: This study develops a theoretical paradigm and a new conceptual parameter for quantitatively calculating and predicting the thermal stability of sulfide solid electrolytes. Experimental strategies and stoichiometric ratio control are used to improve the thermal stability of sulfide solid electrolytes based on the predictions obtained from the derived theory. The potential doping elements to enhance the thermal stability of sulfide solid electrolytes are also screened, and the predicted trends align well with experimental evidence.
Article
Chemistry, Physical
Cody M. Sterling, Chinnathambi Kamal, Alberto Garcia-Fernandez, Gabriel J. Man, Sebastian Svanstrom, Pabitra K. Nayak, Sergei M. Butorin, Hakan Rensmo, Ute B. Cappel, Michael Odelius
Summary: In this study, the electronic structures of methylammonium lead triiodide (MAPI) and methylammonium iodide (MAI) were examined using ab initio molecular dynamics simulations and experimental techniques. The results reveal that the difference in band gap between MAPI and MAI is mainly caused by interactions between iodine and lead.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Jiaxin Ning, Donald G. Truhlar
Summary: The geometries, spin states, and bonding characteristics of NdO2 and SmO22+ were studied and compared using spin-orbit-free wave functions. The ground spin states and structures were found to be different for the two molecules, with NdO2 favoring a linear ONdO triplet structure and SmO22+ favoring a linear SmOO2+ quintet structure. The bonding characteristics were investigated using state-averaged complete active-space self-consistent-field (SA-CASSCF) calculations, which showed electron transfer from Nd to O in NdO2 but not between Sm and O in SmO22+.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)