Energy decomposition analysis

Abstract

The energy decomposition analysis (EDA) is a powerful method for a quantitative interpretation of chemical bonds in terms of three major expressions. The instantaneous interaction energy ΔEint between two fragments A and B in a molecule A–B is partitioned in three terms, namely, (1) the quasiclassical electrostatic interaction ΔEelstat between the fragments, (2) the repulsive exchange (Pauli) interaction ΔEPauli between electrons of the two fragments having the same spin, and (3) the orbital (covalent) interaction ΔEorb, which comes from the orbital relaxation and the orbital mixing between the fragments. The latter term can be decomposed into contributions of orbitals with different symmetry, which makes it possible to distinguish between σ, π, and δ bonding. After a short introduction into the theoretical background of the EDA, we present illustrative examples of main group and transition metal chemistry. The results show that the EDA terms can be interpreted in a chemically meaningful way, thus providing a bridge between quantum chemical calculations and heuristic bonding models of traditional chemistry. © 2011 John Wiley & Sons, Ltd. This article is categorized under: Structure and Mechanism > Molecular Structures

Microwave-Assisted Synthesis and Characterization of [Rh2(OAc)4(L)2] Paddlewheel Complexes: A Joint Experimental and Computational Study

“…All these thermodynamic data suggest that it is possible to incorporate one ligand, but under such conditions, stopping the reaction is not possible (to only obtain 1 -4 ). Moreover, in order to shed more light into the formation of complexes 1-4, we have used an energy decomposition analysis [84,85] for the reaction energy (Δ × ) according to the following equation:…”

Why 1,2-quinone derivatives are more stable than their 2,3-analogues?

“…The latter term is focused on the interaction between the deformed fragments, i.e., the fragments in the geometry they adopt in the studied molecule. ΔE int may be then divided in the framework of the Kohn-Sham MO model by using a quantitative EDA [35][36][37][38][39][40] into electrostatic interaction (ΔV elstat ), Pauli repulsive orbital interactions (ΔE Pauli ), and attractive orbital interactions (ΔE oi ):…”

On Ligand Binding Energies in Porphyrinic Systems

“…EDA methods have been introduced by K. Morokuma and coworkers [14,16,17] and were developed by several groups [2,12,33,34]. A recent review of the method can be found in [30]. A promising implementation to treat larger systems has been introduced by P. Su and H. Li [27] and is included in the GAMESS code [10,24].…”