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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Modeling Singlet Fission in Rylene and Diketopyrrolopyrrole Derivatives: The Role of the Charge Transfer State in Superexchange and Excimer Formation
TL;DR: In this article, a one-step superexchange model is proposed for Singlet fission in organic photovoltaics, which allows the CT state to act as a virtual state, reducing the effect of large Gibbs free energy values from SF rate calculations.
Journal ArticleDOI
A Short BiBi Bond Supported by a Metalloid Group 13 Ligand
Ganesan Prabusankar,Christian Gemel,Pattiyil Parameswaran,Charity Flener,Gernot Frenking,Roland A. Fischer +5 more
Journal ArticleDOI
Multielectron redox chemistry of iron porphyrinogens.
Julien Bachmann,Daniel G. Nocera +1 more
TL;DR: The results reported herein establish a metal-macrocycle cooperativity that engenders a multielectron chemistry for iron porphyrinogens that is unavailable to heme cofactors.
Journal ArticleDOI
Solid-state structure dependence of the molecular distortion and spectroscopic properties of the Cu(I) bis(2,9-dimethyl-1,10-phenanthroline) ion.
TL;DR: The relation between the geometry and spectroscopic properties of a series of salts of the Cu(I) bis(2,9-dimethyl-1,10-phenanthroline) ion, (Cu((I))(dmp)(2))(+), is explored and no correlation is found between ground state geometry and luminescence lifetimes.
Journal ArticleDOI
Au36(SPh)24 nanomolecules: X-ray crystal structure, optical spectroscopy, electrochemistry, and theoretical analysis.
Praneeth Reddy Nimmala,Stefan Knoppe,Vijay Reddy Jupally,Jared H. Delcamp,Christine M. Aikens,Amala Dass +5 more
TL;DR: The results support the idea that a stable core remains intact even when the capping ligand is varied, and show that ESI mass spectrometry gives the correct assignment of Au36(SPh)24, supporting the X-ray crystal structure.
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.