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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Gas-phase chemistry of actinides ions: new insights into the reaction of UO+ and UO2+ with water.
TL;DR: The ability of uranium monoxide cations, UO+ and UO2+, to activate the O-H bond of H2O was studied by using two different approaches of the density functional theory, using relativistic small-core pseudopotentials and B3LYP hybrid functional.
Journal ArticleDOI
Formation and Characterization of a Molecule–Metal–Molecule Bridge in Real Space
TL;DR: This study demonstrates that the combination of STM imaging and spectroscopy enables a direct quantification of the interplay of geometry and electronic coupling in metal-organic complexes in real space.
Journal ArticleDOI
On the origin of optical activity in tris-diamine complexes of Co(III) and Rh(III): a simple model based on time-dependent density function theory.
TL;DR: Time-dependent density functional theory (TD-DFT) is applied to the CD spectra of Lambda(deltadeltadelta)-(+)-[Co(S-pn)n(en)(3-n)]3+ as well as the stereoisomers Delta-(+-)-[ Co(en)3]3+.
Journal ArticleDOI
PyADF — A scripting framework for multiscale quantum chemistry
Christoph R. Jacob,S. Maya Beyhan,Rosa E. Bulo,André Severo Pereira Gomes,Andreas W. Götz,Karin Kiewisch,Jetze Sikkema,Lucas Visscher +7 more
TL;DR: PYADF handles all steps necessary in a typical workflow in quantum chemistry and is easily extensible due to its object‐oriented implementation in the Python programming language.
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Mechanochemical Synthesis of Methylammonium Lead Mixed–Halide Perovskites: Unraveling the Solid-Solution Behavior Using Solid-State NMR
Abhoy Karmakar,Abdelrahman M. Askar,Guy M. Bernard,Victor V. Terskikh,Michelle Ha,Sahil Patel,Karthik Shankar,Karthik Shankar,Vladimir K. Michaelis +8 more
TL;DR: In this paper, the authors demonstrate the ability to readily and stoichiometrically tune the halide composition in methylammonium-based mixed-halide lead perovskite (MHP) materials using a mechanochemical synthesis approach.
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.
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.
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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.