Relativistic effects in structural chemistry
About: This article is published in Chemical Reviews.The article was published on 1988-05-01. It has received 2580 citations till now. The article focuses on the topics: Relativistic quantum chemistry.
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University of Udine1, International School for Advanced Studies2, National Research Council3, Massachusetts Institute of Technology4, University of Paris5, Princeton University6, University of Minnesota7, ParisTech8, University of Milan9, International Centre for Theoretical Physics10, University of Paderborn11, ETH Zurich12, École Polytechnique Fédérale de Lausanne13
TL;DR: QUANTUM ESPRESSO as discussed by the authors is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave).
Abstract: QUANTUM ESPRESSO is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density-functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave). The acronym ESPRESSO stands for opEn Source Package for Research in Electronic Structure, Simulation, and Optimization. It is freely available to researchers around the world under the terms of the GNU General Public License. QUANTUM ESPRESSO builds upon newly-restructured electronic-structure codes that have been developed and tested by some of the original authors of novel electronic-structure algorithms and applied in the last twenty years by some of the leading materials modeling groups worldwide. Innovation and efficiency are still its main focus, with special attention paid to massively parallel architectures, and a great effort being devoted to user friendliness. QUANTUM ESPRESSO is evolving towards a distribution of independent and interoperable codes in the spirit of an open-source project, where researchers active in the field of electronic-structure calculations are encouraged to participate in the project by contributing their own codes or by implementing their own ideas into existing codes.
19,985 citations
TL;DR: In this paper, the DMol3 local orbital density functional method for band structure calculations of insulating and metallic solids is described and the method for calculating semilocal pseudopotential matrix elements and basis functions are detailed together with other unpublished parts of the methodology pertaining to gradient functionals and local orbital basis sets.
Abstract: Recent extensions of the DMol3 local orbital density functional method for band structure calculations of insulating and metallic solids are described. Furthermore the method for calculating semilocal pseudopotential matrix elements and basis functions are detailed together with other unpublished parts of the methodology pertaining to gradient functionals and local orbital basis sets. The method is applied to calculations of the enthalpy of formation of a set of molecules and solids. We find that the present numerical localized basis sets yield improved results as compared to previous results for the same functionals. Enthalpies for the formation of H, N, O, F, Cl, and C, Si, S atoms from the thermodynamic reference states are calculated at the same level of theory. It is found that the performance in predicting molecular enthalpies of formation is markedly improved for the Perdew–Burke–Ernzerhof [Phys. Rev. Lett. 77, 3865 (1996)] functional.
8,496 citations
TL;DR: The construction of transferable, hierarchical basis sets are demonstrated, allowing the calculation to range from qualitative tight-binding like accuracy to meV-level total energy convergence with the basis set, since all basis functions are strictly localized.
2,178 citations
2,151 citations
TL;DR: The ability of platinum and gold catalysts to effect powerful atom-economic transformations has led to a marked increase in their utilization and the application of platinum- and gold-catalyzed transformations in natural product synthesis is discussed.
Abstract: The ability of platinum and gold catalysts to effect powerful atom-economic transformations has led to a marked increase in their utilization. The quite remarkable correlation of their catalytic behavior with the available structural data, coordination chemistry, and organometallic reactivity patterns, including relativistic effects, allows the underlying principles of catalytic carbophilic activation by π acids to be formulated. The spectrum of reactivity extends beyond their utility as catalytic and benign alternatives to conventional stoichiometric π acids. The resulting reactivity profile allows this entire field of catalysis to be rationalized, and brings together the apparently disparate electrophilic metal carbene and nonclassical carbocation explanations. The advances in coupling, cycloisomerization, and structural reorganization—from the design of new transformations to the improvement to known reactions—are highlighted in this Review. The application of platinum- and gold-catalyzed transformations in natural product synthesis is also discussed.
1,938 citations
References
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Book•
01 Jan 1973
TL;DR: In this article, the transition elements involving metal-metal bonds are defined and an introductory essay is given, along with a discussion of homogeneous catalysis and transition metal chemistry, B L Shaw & N I Tucker.
Abstract: (partial) The lanthanides, T Moeller. Carbonyls, cyanides, isocyanides and nitrosyls, W P Griffith. Compounds of the transitional elements involving metal-metal bonds, D L Kepert. Transition metal, J C Green & M V H Green. Nonstoichiometric compounds. An introductory essay, D J M Bevan. Tungsten bronzes, vanadium bronzes and related compounds, P Hagenmuller. Isopolyanions and Heteropolyanions, D L Kepert. Ionic compounds, G C Allen. Transition metal chemistry, B F G Johnson. Organo-transition metal compounds and related aspects of homogenous catalysis, B L Shaw & N I Tucker.
3,003 citations
Book•
01 Jan 1985
TL;DR: In this article, the authors introduce the concept of molecular orbitals of Diatomic Molecules and Electronegativity Perturbation, and propose a method to construct a molecular orbital construction from fragments of small building blocks.
Abstract: Atomic and Molecular Orbitals. Concepts of Bonding and Orbital Interaction. Perturbational Molecular Orbital Theory. Symmetry Considerations. Molecular Orbital Construction from Fragment Orbitals. Molecular Orbitals of Diatomic Molecules and Electronegativity Perturbation. Molecular Orbitals and Geometrical Perturbations. State Wavefunctions and State Energies. Molecular Orbitals of Small Building Blocks. Molecules with Two Heavy Atoms. Orbital Interactions Through Space and Through Bonds. Polyenes and Conjugated Systems. Solids. Hypervalent Molecules. Transition Metal Complexes: A Starting Point at the Octahedron. Square Planar, Tetrahedral ML4 Complexes and Electron Counting. Five Coordination. The C2v ML3 Fragment. The ML2 and ML4 Fragments. Complexes of ML3, MCp and Cp2?M. The Isolobal Analogy. Cluster Compounds.
920 citations
Book•
01 Jun 1984
TL;DR: In this article, the Weizsacker Term, its corrections and Virial Partitioning in Density Functional Theory are discussed. But the authors focus on the second order reduced Density Matrix and the Chemimal Bond.
Abstract: Fundamental Theory.- Density Functional Theory and Local Potential Approximations from Momentum Space Considerations.- Aspects of Density Functional Theory.- On the Calculation of Potentials from Densities.- The Chemical Potential for Interacting Fermions in a Harmonic Potential.- Density, Total Energy and Chemical Potential of Atomic Ions and some Molecules.- Some Aspects of the Role of Single-Particle Density in Chemistry.- The Mechanics of and an Equation for the Electronic Charge Density.- The Qualitative Theory of the Current Density in Molecules.- The Constrained Search Approach, Mappings to External Potentials, and Virial-Like Theorems for Electron-Density and One-Matrix Energy-Functional Theories.- Self-Interaction Correction.- Some Approaches to Density Functional Theory.- Exchange-Correlation Energy Functionals in the Density Functional Formalism.- An Approach to Electron Correlation beyond the Local Spin Density Approximation.- Pair Correlation Energies and Local Spin-Density Functionals.- On the Extension of the Statistical Energy Expression to Multi-Determinantal Wave Functions.- The Weizsacker Term, its Corrections and Virial Partitioning in Density Functional Theory.- The Second Order Reduced Density Matrix and the Chemimal Bond.- Characteristic Function Approach to Density Matrix Calculations.- On the Systematic Assessment of Correlation Effects in Local Density Models.- Relativistic Density Functional Theory.- A Phase Space Approach to Energy Densities in Position Space.- Applications.- Application of the Hartree-Fock-Slater Method in Photoelectron Spectroscopy.- SCF-X?-SW Cluster Molecular-Orbital Models of Catalysts, Alloys, Magnetic Materials, and Superconductors.- Some Applications of the Density-Functional Formalism to Chemisorption.- Density Functional Calculations for Atomic Clusters.- Cohesive Energy, Spectroscopic, and Magnetic Properties of Small Clusters.- Calculations of Hyperfine Interactions in Transition Metal Compounds in the Local Density Approximation.- Local Density Approach to Surfaces and Adsorbed Layers.- Electron Densities in Solid Compounds.- Local Density Approximations for Relativistic Exchange Energies.- Relativistic Multiple Scattering X? Calculations.- Dirac Scattered Wave Calculations.- Theoretical Valence Charge Densities for Graphite, Diamond and LiC6.- Dependence of the Self-Consistent One-Electron Density of Anisotropic Semiconductors on Local Density Approximations.- ?-Ray Bragg and Compton Scattering Experiments Used as Tests of the Validity of the Local Density Approximation.- Multipole Expansion as an Alternative Representation of Charge Density.- Measured Electron Density Distributions in Crystals as a Basis for Band Structure Calculations.- Observation of Electron Distributions on Outermost Layers of Solid Surfaces by Penning Ionization Electron Spectroscopy.- Observations of Local Electron Distributions in Molecular Orbitals.- Accurate Hellmann-Feynman Force Method for the Study of the First and Second Derivatives of Potential Energy Hypersurface.- The Calculation of Spectroscopic Data by the SCC-X? Method.- On Correlated One-Electron Energies in the HFS and HFG Schemes.- On the Atomic Wavefunctions Generated by the Hartree-Fock-Slater Method X?HF and the Modified Hartree-Fock-Slater Method ?aHF which Includes Self Interaction Explicitly.- Ab-Initio Calculations Incorporating Desirable Options for Large Molecules and Solids: a Competitive Completely General Alternative to Local Density Methods for Many Systems.
218 citations