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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Au34-: A Fluxional Core−Shell Cluster
Xiao Gu,Satya S. Bulusu,Xi Li,Xi Li,Xiao Cheng Zeng,Jun Li,Xingao Gong,Lai S. Wang,Lai S. Wang +8 more
TL;DR: In this paper, a structural search at several levels of density functional and ab initio theory revealed that the low-lying isomers of Au34- can be characterized as fluxional core−shell type structures with 4 or 3 inner atoms and 30 or 31 outer atoms.
Journal ArticleDOI
Electron Transfer and Electron Exchange between [Cp*(dppe)Fe] n + ( n = 0, 1) Building Blocks Mediated by the 9,10-Bis(ethynyl)anthracene Bridge
Frédéric de Montigny,Gilles Argouarch,Karine Costuas,Jean-François Halet,Thierry Roisnel,Loïc Toupet,Claude Lapinte +6 more
TL;DR: A bisiron alkynyl-bridged complex, Cp*(dppe)Fe(C-9,10-ant-C⋮C)Fe*(Dppe)Cp*, 10 (ant = anthracene), was synthesized and characterized by X-ray crystal structures.
Journal ArticleDOI
"Open rather than closed" malonate methano-fullerene derivatives. The formation of methanofulleroid adducts of Y3N@C80.
Olena Lukoyanova,Claudia M. Cardona,José Rivera,† Leyda Z. Lugo-Morales,Christopher J. Chancellor,Marilyn M. Olmstead,Antonio Rodríguez-Fortea,Josep M. Poblet,A. L. Balch,Luis Echegoyen +9 more
TL;DR: Density functional theory calculations are presented, which provide a rationale for the formation of the fulleroid and reveal the underlying thermodynamic basis for their stability.
Journal ArticleDOI
Simultaneous elimination of cationic uranium(VI) and anionic rhenium(VII) by graphene oxide–poly(ethyleneimine) macrostructures: a batch, XPS, EXAFS, and DFT combined study
Zhiwei Huang,Zhiwei Huang,Zijie Li,Qun-Yan Wu,Lirong Zheng,Limin Zhou,Zhifang Chai,Xiaolin Wang,Wei-Qun Shi +8 more
TL;DR: In this paper, a 3D graphene oxide-supported ethyleneimine polymer composite (GO-PEI) was synthesized by a self-assembly strategy and used for the simultaneous removal of cationic U(VI) and anionic Re(VII), which acts as a surrogate for Tc(VI), from aqueous solution.
Journal ArticleDOI
Influence of halogen atoms on a homologous series of bis-cyclometalated iridium(III) complexes
Etienne Baranoff,Basile F. E. Curchod,Filippo Monti,Frédéric Steimer,Gianluca Accorsi,Ivano Tavernelli,Ursula Rothlisberger,Rosario Scopelliti,Michael Grätzel,Md. K. Nazeeruddin +9 more
TL;DR: According to theoretical geometries for the lowest triplet state, the large halogen substituents contribute to sizable distortions of specific phenylpyridine ligands for ClIrPic and BrIrPic, which are likely to play a role in the emissive and nonradiative properties when coupled with the heavy-atom effect.
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.