scispace - formally typeset
Journal ArticleDOI

Chemistry with ADF

Reads0
Chats0
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, 2001

read more

Citations
More filters
Journal ArticleDOI

Azaboradibenzo[6]helicene: Carrier Inversion Induced by Helical Homochirality

TL;DR: Azaboradibenzo[6]helicene, a new semiconductor material possessing helical chirality, has been synthesized via a tandem bora-Friedel-Crafts-type reaction, observing unprecedented carrier inversion between the racemate and the single enantiomer.
Journal ArticleDOI

Living Copolymerization of Ethylene with Norbornene Catalyzed by Bis(Pyrrolide−Imine) Titanium Complexes with MAO

TL;DR: Transmission electron microscopy indicated that the PE-b-poly(ethylene-co-norbornene) possesses high potential as a new material consisting of crystalline and amorphous segments which are chemically linked.
Journal ArticleDOI

Reactivity and regioselectivity in 1,3-dipolar cycloadditions of azides to strained alkynes and alkenes: a computational study.

TL;DR: A survey of benzyl azide cycloadditions to substituted cyclooctynes showed that fluorine substitution has the most dramatic effect on reactivity, and Cycloalkynes are predicted to be significantly more reactive dipolarophiles than cycloalkenes.
Journal ArticleDOI

Reversible CO Binding Enables Tunable CO/H2 and CO/N2 Separations in Metal–Organic Frameworks with Exposed Divalent Metal Cations

TL;DR: The reversible CO binding suggests that these frameworks may be of utility for the separation of CO from various industrial gas mixtures, including CO/H2 and CO/N2, and selectivities determined from gas adsorption isotherm data using ideal adsorbed solution theory (IAST) indicate that all six M2(dobdc) frameworks could potentially be used as solid adsorbents to replace current cryogenic distillation technologies.
Journal ArticleDOI

Size-dependence of the enhanced Raman scattering of pyridine adsorbed on Agn (n = 2-8, 20) clusters

TL;DR: In this paper, a time-dependent density functional theory (TDDFT) study of the size-dependence of the absorption and Raman scattering properties of pyridine interacting with small silver nanoclusters Agn (n = 2−8, 20) is presented.
References
More filters
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

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.

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.
Related Papers (5)