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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Copper-phthalocyanine based metal-organic interfaces: The effect of fluorination, the substrate, and its symmetry
Dimas G. de Oteyza,A. El-Sayed,Juan María García-Lastra,E. Goiri,Tobias N. Krauss,Ayse Turak,Esther Barrena,Helmut Dosch,Helmut Dosch,J. Zegenhagen,Angel Rubio,Yutaka Wakayama,José Ortega +12 more
TL;DR: Comparison of the properties of these systematically varied metal-organic interfaces provides new insight into the effect of each of the previously mentioned parameters on the molecule-substrate interactions.
Journal ArticleDOI
A Density Functional Embedded Cluster Study of Proposed Active Sites in Heterogeneous Ziegler−Natta Catalysts
TL;DR: In this paper, a number of different models of the active sites in TiCl4/MgCl2 heterogeneous Ziegler−Natta catalysts were examined using density functional methods.
Journal ArticleDOI
Bisboronic Acids for Selective, Physiologically Relevant Direct Glucose Sensing with Surface-Enhanced Raman Spectroscopy
Bhavya Sharma,Bhavya Sharma,Pradeep Bugga,Lindsey R. Madison,Anne Isabelle Henry,Martin G. Blaber,Nathan G. Greeneltch,Naihao Chiang,Milan Mrksich,George C. Schatz,Richard P. Van Duyne +10 more
TL;DR: The direct sensing of glucose at physiologically relevant concentrations with surface-enhanced Raman spectroscopy (SERS) on gold film-over-nanosphere (AuFON) substrates functionalized with bisboronic acid receptors demonstrates the combination of selectivity and spectral resolution that allow the sensors to resolve glucose in high backgrounds of fructose.
Journal ArticleDOI
Embedded density functional theory for covalently bonded and strongly interacting subsystems
TL;DR: In this paper, a general implementation of the Exact Embedding (EE) method is presented to calculate the large contributions of the nonadditive kinetic potential (NAKP) in such applications.
Journal ArticleDOI
Sc2S@C(s)(10528)-C72: a dimetallic sulfide endohedral fullerene with a non isolated pentagon rule cage.
Ning Chen,Christine M. Beavers,Marc Mulet-Gas,Antonio Rodríguez-Fortea,Elias J. Munoz,Yu Yang Li,Marilyn M. Olmstead,Alan L. Balch,Josep M. Poblet,Luis Echegoyen +9 more
TL;DR: It is concluded that both the transfer of four electrons to the cage and the geometrical requirements of the encaged Sc(2)S cluster play important roles in the stabilization of the C(s)(10528)-C(72) cage.
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.