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Benchmark-Quality Semiexperimental Structural Parameters of van der Waals Complexes.

P Kraus1, D A Obenchain1, I Frank1

  • 1Institut für Physikalische Chemie und Elektrochemie, Leibniz Universität Hannover , Callinstraße 3A, 30167 Hannover, Germany.

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Summary

This study provides benchmark-quality equilibrium geometries for 16 noncovalent complexes, crucial for evaluating computational chemistry methods. The data aids in accurately predicting molecular structures beyond just energies.

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Molecular Modeling

Background:

  • Accurate computational methods require reliable data sets for benchmarking.
  • Focus on relative energies often overshadows the importance of accurate equilibrium geometries.

Purpose of the Study:

  • To create a benchmark-quality data set of semiexperimental equilibrium geometries for noncovalent complexes.
  • To facilitate the direct comparison of computed geometries with high-accuracy experimental data.

Main Methods:

  • Utilizing high-accuracy spectroscopic data.
  • Incorporating vibrational corrections at the double-hybrid density functional level.
  • Obtaining counterpoise-corrected geometries up to the Coupled Cluster Singles Doubles (CCSD) level.

Main Results:

  • A data set of 16 noncovalent complexes with benchmark-quality semiexperimental equilibrium geometries.
  • Inclusion of various interactions: dispersion, hydrogen bonding, and CH/π···π interactions.
  • Analysis of computational method performance, including dispersion-corrected functionals.

Conclusions:

  • The developed data set complements existing resources for computational chemistry benchmarking.
  • Accurate equilibrium geometries are vital for validating computational models of noncovalent interactions.