Journal ArticleDOI
Chemistry with ADF
G. te Velde,F.M. Bickelhaupt,Evert Jan Baerends,C. Fonseca Guerra,S. J. A. van Gisbergen,J.G. Snijders,T. Ziegler +6 more
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TLDR
The “Activation‐strain TS interaction” (ATS) model of chemical reactivity is reviewed as a conceptual framework for understanding how activation barriers of various types of reaction mechanisms arise and how they may be controlled, for example, in organic chemistry or homogeneous catalysis.Abstract:
We present the theoretical and technical foundations of the Amsterdam Density Functional (ADF) program with a survey of the characteristics of the code (numerical integration, density fitting for the Coulomb potential, and STO basis functions). Recent developments enhance the efficiency of ADF (e.g., parallelization, near order-N scaling, QM/MM) and its functionality (e.g., NMR chemical shifts, COSMO solvent effects, ZORA relativistic method, excitation energies, frequency-dependent (hyper)polarizabilities, atomic VDD charges). In the Applications section we discuss the physical model of the electronic structure and the chemical bond, i.e., the Kohn–Sham molecular orbital (MO) theory, and illustrate the power of the Kohn–Sham MO model in conjunction with the ADF-typical fragment approach to quantitatively understand and predict chemical phenomena. We review the “Activation-strain TS interaction” (ATS) model of chemical reactivity as a conceptual framework for understanding how activation barriers of various types of (competing) reaction mechanisms arise and how they may be controlled, for example, in organic chemistry or homogeneous catalysis. Finally, we include a brief discussion of exemplary applications in the field of biochemistry (structure and bonding of DNA) and of time-dependent density functional theory (TDDFT) to indicate how this development further reinforces the ADF tools for the analysis of chemical phenomena. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 931–967, 2001read more
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Cyclometalated iridium(III) complexes based on phenyl-imidazole ligand.
Etienne Baranoff,Simona Fantacci,Filippo De Angelis,Xianxi Zhang,Rosario Scopelliti,Michael Grätzel,Khaja Nazeeruddin +6 more
TL;DR: These series show that modifying the substitution pattern on the ligands can alter the photophysical and electrochemical properties of the complexes, and it is shown that compared to complexes containing phenyl-pyridine ligands, highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular Orbitals (LUMOs) are more delocalized over the entire main ligand in complexes containing Phenyl-imidazole.
Journal ArticleDOI
Surface Complexation of Cu on Birnessite (δ-MnO2): Controls on Cu in the Deep Ocean
TL;DR: In this paper, the authors measured the sorption of Cu on δ-MnO2 as a function of pH and surface loading and developed a surface complexation model (in the basic Stern approximation).
Journal ArticleDOI
A discrete solvent reaction field model within density functional theory
TL;DR: In this article, a discrete reaction field model within Density functional theory (DFT) for studying solvent effects on molecules is presented. But the model is not suitable for the case of water in aqueous solution, and it is found that the inclusion of solvent polarization is essential for an accurate description of dipole and quadrupole moments in the liquid phase.
Journal ArticleDOI
Critical Evaluation of Implicit Solvent Models for Predicting Aqueous Oxidation Potentials of Neutral Organic Compounds.
TL;DR: A baseline assessment provides a compiled benchmark test set of vetted experimental data that may be used to judge newly developed solvation models for their ability to produce improved predictions for aqueous oxidation potentials and related properties.
Journal ArticleDOI
Third Row Transition Metal Hexafluorides, Extraordinary Oxidizers, and Lewis Acids: Electron Affinities, Fluoride Affinities, and Heats of Formation of WF6, ReF6, OsF6, IrF6, PtF6, and AuF6
Raluca Craciun,Desiree Picone,Rebecca T. Long,Shenggang Li,David A. Dixon,Kirk A. Peterson,Karl O. Christe +6 more
TL;DR: High level electronic structure calculations were used to evaluate reliable, self-consistent thermochemical data sets for the third row transition metal hexafluorides, and optimized geometries of the corresponding MF(7)(-) anions were found with a very weak external F-F bond between an MF(6)(-) fragment and a fluorine atom.
References
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Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
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Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
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Self-Consistent Equations Including Exchange and Correlation Effects
Walter Kohn,L. J. Sham +1 more
TL;DR: In this paper, the Hartree and Hartree-Fock equations are applied to a uniform electron gas, where the exchange and correlation portions of the chemical potential of the gas are used as additional effective potentials.
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Density-functional exchange-energy approximation with correct asymptotic behavior.
TL;DR: This work reports a gradient-corrected exchange-energy functional, containing only one parameter, that fits the exact Hartree-Fock exchange energies of a wide variety of atomic systems with remarkable accuracy, surpassing the performance of previous functionals containing two parameters or more.
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Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation.
John P. Perdew,J. A. Chevary,S. H. Vosko,Koblar A. Jackson,Mark R. Pederson,David J. Singh,Carlos Fiolhais +6 more
TL;DR: A way is found to visualize and understand the nonlocality of exchange and correlation, its origins, and its physical effects as well as significant interconfigurational and interterm errors remain.