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
Reversible disorder-order transitions in atomic crystal nucleation.
Sungho Jeon,Taeyeong Heo,Sang-Yeon Hwang,Jim Ciston,Karen C. Bustillo,Bryan W. Reed,Jimin Ham,S. K. Kang,Sungin Kim,Joowon Lim,Kitaek Lim,Ji Soo Kim,Min Ho Kang,Ruth S. Bloom,Sukjoon Hong,Kwanpyo Kim,Alex Zettl,Alex Zettl,Woo Youn Kim,Peter Ercius,Jungwon Park,Won Chul Lee +21 more
TL;DR: In this article, the early stage of atomic crystallization proceeds through dynamic structural fluctuations between disordered and crystalline states, rather than through a single irreversible transition, and experimental and theoretical analyses support the idea that structural fluctuations originate from size-dependent thermodynamic stability of the two states in atomic clusters.
Journal ArticleDOI
A vibrational circular dichroism implementation within a Slater-type-orbital based density functional framework and its application to hexa- and hepta-helicenes
TL;DR: In this paper, the authors describe the implementation of the rotational strengths for vibrational circular dichroism (VCD) in the Slater-type orbital based Amsterdam density functional (ADF) package.
Journal ArticleDOI
ERKALE?A flexible program package for X-ray properties of atoms and molecules
TL;DR: ERKALE is a novel software program for computing X‐ray properties, such as ground‐state electron momentum densities, Compton profiles, and core and valence electron excitation spectra of atoms and molecules, which operates at Hartree–Fock or density‐functional level of theory and supports Gaussian basis sets of arbitrary angular momentum.
Journal ArticleDOI
Experimental and theoretical charge density studies at subatomic resolution.
Andreas Fischer,Davide Tiana,Wolfgang Scherer,Kilian Batke,Georg Eickerling,Helle Svendsen,Niels Bindzus,Bo B. Iversen +7 more
TL;DR: Analysis of accurate experimental and theoretical structure factors of diamond and silicon reveals that the contraction of the core shell due to covalent bond formation causes significant perturbations of the total charge density that cannot be ignored in precise charge density studies.
Journal ArticleDOI
Promoted cobalt metal catalysts suitable for the production of lower olefins from natural gas.
Jingxiu Xie,Pasi P. Paalanen,Tom W. van Deelen,Bert M. Weckhuysen,Manuel J. Louwerse,Krijn P. de Jong +5 more
TL;DR: A Co1Mn3-Na2S catalyst is designed, which has a hydrocarbon product spectrum deviating from the Anderson–Schulz–Flory distribution, and a synergistic effect of Na plus S is proposed, which act as electronic promoters on the Co surface, thus improving selectivities towards lower olefins and fuels while largely reducing methane and carbon dioxide formation.
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.
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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.