On the influence of basis sets and quantum chemical methods on the prediction accuracy of COSMO-RS

文献信息

发布日期 2011-11-02
DOI 10.1039/C1CP22317H
影响因子 3.676
作者

Bernd Hannebauer


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摘要

This paper examines how the accuracy of activity coefficients at infinite dilution calculated from the conductor-like screening model for real solvents (COSMO-RS) depends on the basis set and the quantum chemical method used. Activity coefficients at various temperatures serve as experimental parameters for optimising the COSMO-RS parameters. A modification of the electrostatic misfit term of the energy function of COSMO-RS is presented that leads to a slightly higher accuracy. COSMO-RS parameter sets for nine different systematically varied basis sets using the density functional theory with the BP86 functional show that at least a valence double-zeta basis set is necessary for good accuracy. Larger basis sets show no advantages. Investigations of eight different quantum chemical calculation methods using a valence triple-zeta basis set are documented. Hartree–Fock and local density approximations give relatively poor results. The gradient-corrected density functionals investigated and the B3LYP hybrid functional show practically identical accuracy. The most accurate parameterisation was obtained with MP2.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

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