Kohn‐Sham Density Functional Theory: Predicting and Understanding Chemistry

Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

“…Further details on the EDA can be found in the literature. 90,92 The EDA has been used by us for a comprehensive study of metal-ligand interactions in transition metal complexes. 93,94 Supporting Information Available:…”

“…88,89 The bonding analysis focuses on the instantaneous interaction energy ΔE int of a 90 It comprises the destabilizing interactions between electrons of the same spin on either fragment. The orbital interaction ΔE orb accounts for charge transfer and polarization effects.…”

Reactivity and Selectivity of Bowl‐Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C60

“…Both C 60 and bowl-shaped fullerenes usually prefer [6,6]-bonds over [5,6]-bonds in their reactions, typically, addition and cycloaddition. [3,4] For C 60 , the physical factors behind this extraordinary selectivity were not completely understood until our recent study [10] using the Activation Strain Model (ASM) [11] in combination with quantitative molecular orbital (MO) theory and the Energy Decomposition Analysis (EDA) [12,13] method. We found that, for the [4+2]-cycloaddition reaction between C 60 and cyclopentadiene, the major factor controlling the observed regioselectivity is the stronger interaction between the deformed reactants in the [6,6] reaction pathway along the entire reaction coordinate as a consequence of a more effective <HOMO(cyclopentadiene)|LUMO(fullerene)> molecular overlap involving the 3 [6,6]-pyracylenic C-C bond.…”

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

“…General theoretical background on the bond energy decomposition scheme used here (Morokuma-Ziegler) can be found in the papers by Bickelhaupt and Baerends [39,41]. Finally, in the EDA of the bonding energy, open-shell fragments were treated with the spin-unrestricted formalism, but for technical reasons, spin polarization cannot be included.…”

“…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 ):…”