Review
Chemistry, Multidisciplinary
Geneva Laurita, Ram Seshadri
Summary: The lone pair, a known feature of molecular electronic structure, plays a significant role in the crystalline solid state, with impacts on various properties and functionalities. It affects ion transport, dipole formation, refractive index, thermal conductivity, and light generation. Recent studies have recognized its role in the electronic structure of topological quantum materials. Hidden lone pairs, characterized by local distortions, have become a growing area of research. This Account introduces the chemistry of lone pairs in extended crystalline solids, discussing their stereochemical activity, manifestation in structure, and tuning by the chemical environment.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Physical
Joseph Handy, Wasif Zaheer, Arianna R. M. Rothfuss, Caitlin R. McGranahan, George Agbeworvi, Justin L. Andrews, Karoline E. Garcia-Pedraza, John D. Ponis, Jaime R. Ayala, Yu Ding, David F. Watson, Sarbajit Banerjee
Summary: With the current economic growth and consumption trends, the world is facing a major issue of global warming caused by greenhouse gas emissions. To combat climate change, it is crucial to decarbonize the transportation infrastructure and develop efficient photocatalytic architectures that can utilize water or CO2 to store solar energy. This perspective article introduces a palette of heterostructures designed for direct solar-driven water splitting and CO2 reduction, which involve the use of quantum dots and vanadium oxide compounds. The design principles and synthetic strategies for these heterostructures are discussed, along with the potential application of machine learning and high-throughput synthesis in materials design.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Alina F. Saifina, Sergey V. Kartashov, Adam I. Stash, Vladimir G. Tsirelson, Robert R. Fayzullin
Summary: This paper presents a binding approach based on the electrostatic and kinetic force density fields to explain interatomic interactions, structures, and chemical reactions. The study investigates various aspects including the arrangement of zero-flux surfaces, compression of force-field pseudoatoms, penetration of bonded atoms, distortion of force fields, and binding paths. The concept of force-induced push-pull assembling of interacting atoms is introduced, and the force-based binding structure is proposed. The crystal structures of chalcogen and tetrel bonding resemble the initial and transition states of nucleophilic substitution reactions.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Biochemistry & Molecular Biology
Julen Munarriz, Miguel Gallegos, Julia Contreras-Garcia, Angel Martin Pendas
Summary: The interacting quantum atoms approach is used to examine energetic descriptors for rationalizing substituent effects in electrophilic aromatic substitutions. The decay mode of aromatic valence bond basin populations and the fluctuation of adjacent bonds can provide information about inductive and mesomeric effects. The kinetic energy of electrons in aromatic basins, as well as their mutual exchange-correlation energies, are proposed as suitable energetic indices containing relevant substituent effects information.
Article
Multidisciplinary Sciences
Yan Liu, Rui Wang, Zhigang Wang, Da Li, Tian Cui
Summary: In this study, the authors report the prediction of a nitrogen-rich iodine nitride compound (IN6) with an unusual twelve-fold coordination of the iodine atom under high pressure. They discovered the existence of a hypercoordinated IN6 compound composed of N-6 rings and an unusual iodine-nitrogen covalent bond network using particle swarm optimization method and first-principles calculations. The formation of twelve-fold iodine hypercoordination is facilitated by the presence of high pressure and N-6 rings. The findings also suggest that halogen elements with lower atomic numbers have weaker valence expansion propensity in halogen nitrides.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Andrei V. Afonin, Valentin A. Semenov, Alexander V. Vashchenko
Summary: The parameters of the critical point near a heteroatom in the localized orbital locator topology reflect changes in size, density and energy of the lone pair, and are correlated with the donor ability of the lone pair carrying the heteroatom.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Corentin Lefebvre, Hassan Khartabil, Eric Henon
Summary: We introduce a new concept called the atomic degree of interaction (DOI), which is based on the electron density-based independent gradient model (IGM). DOI captures any manifestation of electron density sharing around an atom and reflects the attachment strength of the atom to its molecular neighborhood. It is found to be sensitive to the local chemical environment of the atom. While there is no significant correlation between atomic DOI and other atomic properties, a strong connection has been established between this electron density-based index and the scalar reaction path curvature in the H-2 + H reacting system.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Logan Epperson, Megan Mascarenas, Amanda Morgenstern
Summary: Applying an electric field to molecules induces rearrangement of their electron charge density. Understanding how electric fields rearrange this density is crucial for incorporating electric fields into experimental design. To gain this understanding, electric fields were applied to a set of molecules, and an analysis called gradient bundle analysis was employed to quantify the redistribution of electron charge density. The results showed relationships between the redistributed densities and various molecular properties.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Lakhya J. Mazumder, Amlan J. Kalita, Shahnaz S. Rohman, Chayanika Kashyap, Sabnam S. Ullah, Indrani Baruah, Ashapurna Boro, Ankur K. Guha, Pankaz K. Sharma
Summary: The study investigates unsupported donor-acceptor complexes of noble gases with group 13 elements using density functional theory. It finds that heavier noble gases can form thermodynamically stable compounds. The research suggests that prepyramidalization at the Lewis acid center may be an interesting alternative to stabilize these complexes, instead of requiring a rigid framework.
Article
Chemistry, Physical
Amlan J. Kalita, Siddhartha K. Purkayastha, Kangkan Sarmah, Ankur K. Guha
Summary: The Lewis basic character of alkali metals forming donor-acceptor complexes is very rare, and no Lewis adduct with an alkalide as the Lewis basic centre has been reported. In this study, we theoretically designed clusters of EXH2- (E = Li, Na, K; X = Be, Mg, Ca), which represent the first true examples of Lewis adducts with alkalides as the two-electron donor basic sites. Our calculations reveal the formation of an unprecedented E:(-) -> XH2 donor-acceptor interaction, which is confirmed by topological analysis. The calculated bond dissociation energies suggest the possibility of spectroscopic identification.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Multidisciplinary Sciences
Carl-Friedrich Schoen, Steffen van Bergerem, Christian Mattes, Aakash Yadav, Martin Grohe, Leif Kobbelt, Matthias Wuttig
Summary: By studying the relationship between the structure of multidimensional property space and chemical bonding mechanisms, quantum chemical bonding descriptors can be transformed into material property predictors, which can be used for inverse material design.
Article
Chemistry, Physical
Nisha Job, Krishnan Thirumoorthy
Summary: The nature of chemical bonding in seven low-lying isomers of SiC4H2 is analyzed using quantum chemical concepts. Four isomers have been identified in the laboratory, while the other three remain elusive. Various bonding analysis tools were employed to gain insight into the characteristics of chemical bonding, revealing the involvement of the lone pair of the silicon atom and its influence on the structural stability of the isomers.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Inorganic & Nuclear
Corinne Lacaze-Dufaure, Yann Bulteau, Nathalie Tarrat, David Loffreda, Pierre Fau, Katia Fajerwerg, Myrtil L. Kahn, Franck Rabilloud, Christine Lepetit
Summary: Amine ligands are expected to drive the organization of metallic centers and the chemical reactivity of silver clusters during the synthesis of silver nanoparticles. Computational studies using density functional theory have characterized the structure and stability of small-size silver clusters with or without ethylamine ligands. The analysis of the Ag-N and Ag-Ag bond energies explains the transition from 2D to 3D structures. Electron transfer from ethylamine to the silver atoms increases the polarization of the metallic core.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Riccardo Freccero, Laura C. J. Pereira, Pavlo Solokha, Serena De Negri
Summary: The RE2PdGe3 (RE = rare-earth metal) series was studied and it was found that Yb2PdGe3 is the only compound with an AlB2 ordered superstructure. Single crystals of Yb2PdGe3 were grown from molten indium flux for accurate investigation. The crystal structure of Yb2PdGe3 was determined to be a four-order derivative of AlB2, with superconducting behavior below 4 K. Magnetic susceptibility measurements indicate a divalent state for Yb, while bonding interactions between Ge were found to be intermediate between single bonds and higher-order bonds.
INORGANIC CHEMISTRY
(2023)
Article
Optics
Bjorn Schrinski, Philipp Haslinger, Jorg Schmiedmayer, Klaus Hornberger, Stefan Nimmrichter
Summary: Precision interferometry with Bose-Einstein condensed atoms can lower the current empirical bound on the localization rate parameter of CSL by focusing on atom count distributions, rather than mean population imbalances. The interplay between CSL-induced diffusion and atom-atom interactions results in an amplified sensitivity of the condensate to CSL.
Article
Chemistry, Physical
Francesco Sessa, Martina Olsson, Fredrik Soderberg, Fang Wang, Martin Rahm
Summary: The quantum mechanically calculable Q descriptor is confirmed to be a powerful tool for quantifying chemical reactivity in complex molecules, with strong correlation to experimental field effects and Hammett parameters. Models for predicting substituent effects are presented and applied, allowing fast estimation and medium-throughput screening of molecules. An experimental dataset is proposed as a benchmark for aiding the development and comparison of electronic structure analyses, specifically in chemical bonding analysis of larger molecules.
Correction
Chemistry, Multidisciplinary
Martin Rahm, Roberto Cammi, N. W. Ashcroft, Roald Hoffmann
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Ashwani Vij, William W. Wilson, Ralf Haiges, Kyle C. Edwards, David A. Dixon, Karl O. Christe
Summary: The crystal structures of [NH3F](+)[CF3SO3](-), [NH2F2](+)[SbF6](-), and [N2F3](+)[Sb3F16](-) have been determined for the first time. The influences of the hybridization of the central nitrogen atom and the number of fluorine substituents on the N-F bond lengths have been evaluated. It is shown that the N-F bond length decreases with increasing fluorine substitution and increasing s-character of the nitrogen atom. Unusual N-F bond lengths reported in previous literature are caused by disorder problems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Francesco Sessa, Martin Rahm
Summary: Controlling the distribution of electrons in materials is a significant goal in chemistry and material science. This work presents a new theory that reinterprets chemical concepts and physical quantities to express the chemical potentials of atoms and molecules. The theory challenges the traditional assumption of electronegativity equalization and provides a different perspective.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Applied
Martin Rahm
Summary: This study uses a scale for pressure-adapted atomic electronegativity to predict bond polarity in compounds experiencing shock conditions, finding that bond polarity generally increases in energetic materials. The study also suggests that changing electronegativity plays a role in the ion disproportionation of molecular phases with compression.
PROPELLANTS EXPLOSIVES PYROTECHNICS
(2023)
Article
Chemistry, Physical
Phalgun Lolur, Marten Skogh, Werner Dobrautz, Christopher Warren, Janka Biznarova, Amr Osman, Giovanna Tancredi, Goran Wendin, Jonas Bylander, Martin Rahm
Summary: This work introduces a strategy called reference-state error mitigation (REM) for quantum chemistry, which can be implemented on current and near-term devices. REM can be applied alongside existing mitigation procedures with minimal post-processing and additional measurements. The method is designed for the variational quantum eigensolver and shows significant improvement in the computational accuracy of ground state energies of small molecules on superconducting quantum hardware. Simulations of noisy circuits with a depth exceeding 1000 two-qubit gates demonstrate the scalability of the method.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Stefano Racioppi, Phalgun Lolur, Per Hyldgaard, Martin Rahm
Summary: In this article, a different calculation method based on energy functional terms is proposed, which partly solves the problem of weak connection between electronic energy and physical quantities in traditional Kohn-Sham (KS) density functional theory (DFT). The calculated average electron energy is close to the experimental ionization potentials (IPs) in one-electron systems, indicating a small impact of self-interaction and other exchange-correlation errors in established DFT methods. Remarkable agreement with ab initio quantum mechanical calculations of multielectron systems is demonstrated using several flavors of DFT, and the average electron energy is argued to be a design criterion for density functional approximations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Multidisciplinary Sciences
Yizhou Yang, Yanyan Chen, Fernando Izquierdo-Ruiz, Clara Schafer, Martin Rahm, Karl Borjesson
Summary: A liquid-liquid interfacial approach based on physical-organic considerations is used to synthesize an ultrathin covalent crystal film, enabling the formation of covalently bonded crystal films on a centimeter size scale with a uniform thickness of 13 nm.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Hilda Sandstrom, Martin Rahm
Summary: We elucidate the mechanisms behind the formation of diaminomaleonitrile and polyimine in liquid HCN using molecular dynamics simulations. These materials are proposed as important intermediates for further chemical evolution. The similar formation rates of these materials provide an explanation of how HCN's self-reactions can quickly diversify under kinetic control. Understanding these reaction routes helps in rationalizing subsequent reactivity in astrochemical environments such as on Titan, comets, exoplanet atmospheres, and the early Earth.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Martin Moebs, David A. Dixon, Gabriel F. de Melo, Monica Vasiliu, Tim Graubner, Karl O. Christe, Florian Kraus
Summary: The purely chemical synthesis of fluorine, previously believed to be impossible, was achieved in 1986 but has not been further studied since then. The mechanism of this reaction has been a mystery until recently, when it was experimentally resolved and supported by electronic structure calculations. These findings clarified the previous discrepancy and showed that the reductive elimination of F-2 requires a large excess of SbF5, occurring in the last reaction step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Alexander I. Kolesnikov, Aravind Krishnamoorthy, Ken-ichi Nomura, Zhongqing Wu, Douglas L. Abernathy, Ashfia Huq, Garrett E. Granroth, Karl O. Christe, Ralf Haiges, Rajiv K. Kalia, Aiichiro Nakano, Priya Vashishta
Summary: The study investigates the structures, properties, and phonon density of iodine oxides I2Oy, providing insights into their potential applications in agent defeat materials.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Marten Skogh, Oskar Leinonen, Phalgun Lolur, Martin Rahm
Summary: In this work, a quantum computational warm-start approach for potential energy surface calculations is evaluated, showing significant speedup compared to calculations relying on a Hartree-Fock initial state. The approach of transferring parameters between similar problems has potential for accelerating quantum chemistry calculations.
ELECTRONIC STRUCTURE
(2023)
Article
Chemistry, Inorganic & Nuclear
Thomas Saal, Ralf Haiges, Karl O. Christe
Summary: The synthesis of trifluoromethylcarboxonium salts through low-temperature protonation was achieved and characterized. These salts are thermally unstable solids, stabilized by hydrogen bonding.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Petter Dunas, Andrew J. Paterson, Gabriele Kociok-Kohn, Martin Rahm, Simon E. Lewis, Nina Kann
Summary: A palladium-catalyzed domino arylation-cyclization of biocatalytically derived cyclic 1,3-dienes has been demonstrated, providing access to tricyclic tetrahydrofluorenones with full regio- and stereoselectivity in a single step. The transformation proceeds through a novel acylation-terminated Heck-type sequence, with quantum chemical calculations indicating the involvement of C-H activation in the terminating acylation step.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Martin Rahm, Paul Erhart, Roberto Cammi
Summary: Compression reveals the connection between van-der-Waals radii and electronegativity, and their relationships to the driving forces behind chemical and physical transformations.
