A Combined Charge and Energy Decomposition Scheme for Bond Analysis

  • Mitoraj M
  • Michalak A
  • Ziegler T
  • 1


    Mendeley users who have this article in their library.
  • N/A


    Citations of this article.


In the present study we have introduced a new scheme for chemical bond analysis by combining the Extended Transition State (ETS) method [Theor. Chim. Acta 1977, 46, 1] with the Natural Orbitals for Chemical Valence (NOCV) theory [J. Phys. Chem. A 2008, 112, 1933; J. Mol. Model. 2007, 13, 347]. The ETS-NOCV charge and energy decomposition scheme based on the Kohn-Sham approach makes it not only possible to decompose the deformation density, ∆F, into the different components (such as σ, π, δ, etc.) of the chemical bond, but it also provides the corresponding energy contributions to the total bond energy. Thus, the ETS-NOCV scheme offers a compact, qualitative, and quantitative picture of the chemical bond formation within one common theoretical framework. Although, the ETS-NOCV approach contains a certain arbitrari-ness in the definition of the molecular subsystems that constitute the whole molecule, it can be widely used for the description of different types of chemical bonds. The applicability of the ETS-NOCV scheme is demonstrated for single (H 3 X-XH 3 , for X) C, Si, Ge, Sn) and multiple (H 2 XdXH 2 , H 3 CXtXCH 3 , for X) C, Ge) covalent bonds between main group elements, for sextuple and quadruple bonds between metal centers (Cr 2 , Mo 2 , W 2 , [Cl 4 CrCrCl 4 ] 4-), and for double bonds between a metal and a main group element ((CO) 5 CrdXH 2 , for X) C, Si, Ge, Sn). We include finally two applications involving hydrogen bonding. The first covers the adenine-thymine base pair and the second the interaction between C-H bonds and the metal center in the alkyl complex.

Get free article suggestions today

Mendeley saves you time finding and organizing research

Sign up here
Already have an account ?Sign in

Find this document


  • Mariusz P Mitoraj

  • Artur Michalak

  • Tom Ziegler

Cite this document

Choose a citation style from the tabs below

Save time finding and organizing research with Mendeley

Sign up for free