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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Vibronic structure of the permanganate absorption spectrum from time-dependent density functional calculations.
TL;DR: The vibronic coupling is investigated by means of linear-response time-dependent density functional calculations and a Taylor series expansion in the normal coordinates of a diabatic potential energy matrix, coupling 24 excited states, which solves the long-standing assignment problem of these bands.
Journal ArticleDOI
β-Diketiminato Nickel Imides in Catalytic Nitrene Transfer to Isocyanides
TL;DR: The β-diketiminato nickel(I) species [Me3NN]Ni(2-picoline) (1) serves as an efficient catalyst for carbodiimide (RN═C═NR′) formation in the reactions of a range of organoazides N3R with isocyanides R′NC.
Journal ArticleDOI
Thienoacene dimers based on the thieno[3,2-b]thiophene moiety: synthesis, characterization and electronic properties
Claude Niebel,Yeongin Kim,Christian Ruzié,Jolanta Karpinska,Basab Chattopadhyay,Guillaume Schweicher,Audrey Richard,Vincent Lemaur,Yoann Olivier,Jérôme Cornil,Alan R. Kennedy,Ying Diao,Wen-Ya Lee,Stefan C. B. Mannsfeld,Zhenan Bao,Yves Geerts +15 more
TL;DR: In this paper, two thienoacene dimers based on the 3,2-bthiophene moiety were efficiently synthesized, characterized and evaluated as active hole-transporting layers in organic thin-film field effect transistors.
Journal ArticleDOI
Mixed-Valence Nickel–Iron Dithiolate Models of the [NiFe]-Hydrogenase Active Site
David Schilter,Mark J. Nilges,Mrinmoy Chakrabarti,Paul A. Lindahl,Thomas B. Rauchfuss,Matthias Stein +5 more
TL;DR: DFT calculations using the BP86, B3LYP, and PBE0 exchange-correlation functionals agree with the structural and spectroscopic data, suggesting that the SOMOs in complexes of the present type are localized in an Fe(I)-centered d(z(2)) orbital.
Journal ArticleDOI
Composition and Constitution of Compressed Strontium Polyhydrides
TL;DR: In this article, the structure of strontium polyhydrides with n > 2 was studied using evolutionary algorithms coupled with density functional theory calculations, and a number of phases with even n were found to be thermodynamically stable below 150 GPa.
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.
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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.