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Molecular single-bond covalent radii for elements 1-118.

Pekka Pyykkö1, Michiko Atsumi

  • 1Department of Chemistry, University of Helsinki, P.O.B. 55 (A.I. Virtasen aukio 1), 00014 Helsinki, Finland. Pekka.Pyykko@helsinki.fi

Chemistry (Weinheim an Der Bergstrasse, Germany)
|December 6, 2008
PubMed
Summary

A new system of additive covalent radii has been developed for all elements in the periodic table, enabling accurate prediction of bond lengths. This method provides a consistent framework for understanding chemical bonding across diverse elements.

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Area of Science:

  • Chemistry
  • Physical Chemistry
  • Quantum Chemistry

Background:

  • Accurate covalent radii are essential for predicting and understanding chemical bond lengths.
  • Existing models for covalent radii have limitations, particularly for certain elements and bonding types.

Purpose of the Study:

  • To establish a self-consistent system of additive covalent radii for the entire periodic table (Groups 1-18, Z=1-118).
  • To incorporate a wide range of experimental and theoretical bond length data for developing the radii system.
  • To provide a unified and accurate method for calculating covalent radii applicable to diverse chemical environments.

Main Methods:

  • Developed a system of additive covalent radii R(AB) = r(A) + r(B) for all elements.
  • Utilized experimental and theoretical primary bond lengths (R) corresponding to chosen group valencies.
  • Incorporated data for homonuclear (E-E), heteronuclear (E-H), and methyl-based (E-CH3) bonds, as well as intra-group E-E' data.
  • Excluded transition-metal halides/chalcogenides and H2/F2 due to complexities suggesting partial multiple bonding.

Main Results:

  • A comprehensive set of covalent radii values (r(E)) was derived for the entire periodic table.
  • The developed system shows good agreement with established models like Pauling's for late main groups and Suresh and Koga's for other elements.
  • Separate fits for diatomic alkali metals and halides achieved very high accuracy.
  • The overall standard deviation for 410 data points was 2.8 pm, indicating high precision.

Conclusions:

  • The established system provides a reliable and self-consistent set of additive covalent radii for all elements.
  • This model offers improved accuracy in predicting bond lengths compared to previous methods, especially when considering a broad range of chemical bonds.
  • The findings contribute to a better fundamental understanding of chemical bonding and atomic sizes across the periodic table.