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Classical Versus Quantum Mechanical Simulations: The Accuracy of Computer Experiments in Solution Chemistry

  • B. M. Rode
  • C. F. Schwenk
  • B. R. Randolf
Chapter
Part of the NATO Science Series book series (NAII, volume 133)

Abstract

Sophisticated simulation techniques in combination with high-speed computing provide a very powerful tool for the elucidation of structural data and dynamics of solutions, which in several aspects can be superior to any experimental technique. A careful analysis and comparison of simulation results achieved at different levels of accuracy shows that classical simulations, even including 3-body corrections, do not supply sufficiently precise data for all structural details and dynamical processes. As simulation techniques based on small clusters and simple density functionals also fail in the prediction of ion solvate structures, mixed quantum mechanical/molecular mechanical (QM/MM) simulations at Hartree-Fock level with medium-sized basis sets appear as the only viable method within today’s computational affordability to achieve the necessary accuracy for a theoretical approach to the details of microspecies structures and their dynamics in electrolyte solutions. Results of QM/MM-MD simulations for numerous main group and transition metal cations presented here exemplify the capability of this method and clearly show the limits not only of classical simulation techniques, but also of the models being used for the interpretation of experimental measurements.

Keywords

Monte Carlo Hydration Shell Aqueous Ammonia Solution Preferential Solvation Hydration Energy 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Springer Science+Business Media Dordrecht 2004

Authors and Affiliations

  • B. M. Rode
    • 1
  • C. F. Schwenk
    • 1
  • B. R. Randolf
    • 1
  1. 1.Department of Theoretical Chemistry, Institute of General, Inorganic and Theoretical ChemistryUniversity of InnsbruckInnsbruckAustria

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