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      Supramolecular Binding Thermodynamics by Dispersion-Corrected Density Functional Theory

      Chemistry - A European Journal
      Wiley

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          Abstract

          The equilibrium association free enthalpies ΔG(a) for typical supramolecular complexes in solution are calculated by ab initio quantum chemical methods. Ten neutral and three positively charged complexes with experimental ΔG(a) values in the range 0 to -21 kcal mol(-1) (on average -6 kcal mol(-1)) are investigated. The theoretical approach employs a (nondynamic) single-structure model, but computes the various energy terms accurately without any special empirical adjustments. Dispersion corrected density functional theory (DFT-D3) with extended basis sets (triple-ζ and quadruple-ζ quality) is used to determine structures and gas-phase interaction energies (ΔE), the COSMO-RS continuum solvation model (based on DFT data) provides solvation free enthalpies and the remaining ro-vibrational enthalpic/entropic contributions are obtained from harmonic frequency calculations. Low-lying vibrational modes are treated by a free-rotor approximation. The accurate account of London dispersion interactions is mandatory with contributions in the range -5 to -60 kcal mol(-1) (up to 200% of ΔE). Inclusion of three-body dispersion effects improves the results considerably. A semilocal (TPSS) and a hybrid density functional (PW6B95) have been tested. Although the ΔG(a) values result as a sum of individually large terms with opposite sign (ΔE vs. solvation and entropy change), the approach provides unprecedented accuracy for ΔG(a) values with errors of only 2 kcal mol(-1) on average. Relative affinities for different guests inside the same host are always obtained correctly. The procedure is suggested as a predictive tool in supramolecular chemistry and can be applied routinely to semirigid systems with 300-400 atoms. The various contributions to binding and enthalpy-entropy compensations are discussed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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          Self-consistent-charge density-functional tight-binding method for simulations of complex materials properties

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            Climbing the density functional ladder: nonempirical meta-generalized gradient approximation designed for molecules and solids.

            The electron density, its gradient, and the Kohn-Sham orbital kinetic energy density are the local ingredients of a meta-generalized gradient approximation (meta-GGA). We construct a meta-GGA density functional for the exchange-correlation energy that satisfies exact constraints without empirical parameters. The exchange and correlation terms respect two paradigms: one- or two-electron densities and slowly varying densities, and so describe both molecules and solids with high accuracy, as shown by extensive numerical tests. This functional completes the third rung of "Jacob's ladder" of approximations, above the local spin density and GGA rungs.
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              Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials

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                Author and article information

                Journal
                Chemistry - A European Journal
                Chem. Eur. J.
                Wiley
                09476539
                August 06 2012
                August 06 2012
                July 10 2012
                : 18
                : 32
                : 9955-9964
                Article
                10.1002/chem.201200497
                22782805
                58f30d82-acd3-4d6b-b314-3fb573dbca54
                © 2012

                http://doi.wiley.com/10.1002/tdm_license_1.1

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