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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Journal ArticleDOI
Interaction of a Bulky N-Heterocyclic Carbene Ligand with Rh(I) and Ir(I). Double C−H Activation and Isolation of Bare 14-Electron Rh(III) and Ir(III) Complexes
TL;DR: Reactivity and structural studies of unusual rhodium and iridium systems bearing two N-heterocyclic carbene (NHC) ligands are presented and DFT calculations show that these electrophilic metal centers are stabilized by pi-donation of the NHC ligands.
Journal ArticleDOI
From Discrete Electronic States to Plasmons: TDDFT Optical Absorption Properties of Agn(n= 10, 20, 35, 56, 84, 120) Tetrahedral Clusters
TL;DR: In this paper, the optical absorption spectra of silver tetrahedral Ag n (n = 10, 20, 35, 56, 84, 120) clusters with emphasis on neutral and ion clusters that correspond to shell closings were calculated.
Book ChapterDOI
Density functional methods for excited states: equilibrium structure and electronic spectra
Filipp Furche,Dmitrij Rappoport +1 more
TL;DR: In this paper, the authors discuss the use of time-dependent density functional theory (DFT) for excited states and present an algorithm to compute spectra and excited state properties.
Journal ArticleDOI
Divalent Carbon(0) Chemistry, Part 2: Protonation and Complexes with Main Group and Transition Metal Lewis Acids
Ralf Tonner,Gernot Frenking +1 more
TL;DR: The calculations show that the experimentally known compounds 2-5 and 8 chemically behave like molecules L(2)C which have two L-->C donor-acceptor bonds and a carbon atom with two electron lone pairs.
Journal ArticleDOI
Synthesis of BN-fused polycyclic aromatics via tandem intramolecular electrophilic arene borylation.
TL;DR: Time-resolved microwave conductivity measurements prove that the intrinsic hole mobility of A is comparable to that of rubrene, one of the most commonly used organic semiconductors, indicating that BN-substituted PAHs are potential candidates for organic electronic materials.
References
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Journal ArticleDOI
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.
Journal ArticleDOI
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.
Journal ArticleDOI
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.
Journal ArticleDOI
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.
Journal ArticleDOI
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.