Bond energy decomposition

Umeyama, H., and Morokuma, K. Origin of hydrogen-bonding energy decomposition study. J.Am. Chem. Soc., 99,1316-1332 (1977). 

ADF calculates various chemically meaningful terms that add up to the bond energy, with an adaptation of Morokuma s bond-energy decomposition to the Kohn-Sham MO method. The individual terms are chemically intuitive quantities such as electrostatic energy, steric repulsion, Pauli repulsion, and orbital interactions. The latter are symmetry decomposed according to the Ziegler transition-state method. ... 

Fig. 7 Bond energy decomposition [Eq. (2)] along the L-M-L angles for Pd(PH3)2 and halogen-substituted Pd(PX3)2 complexes. Dots indicate the position of the minimum on the energy profile. Due to the use of frozen geometries and the omission of dispersion corrections, all minima are shifted to the right. Computed at ZORA-BLYP/TZ2P...

Multiple M=P bonding in (OC)5M=PR becomes evident with ADF s bond energy analysis in terms of electrostatic interactions, Pauli repulsion, and orbital interactions from which the a,Ti-separation is obtained using a symmetry decomposition scheme [21]. For singlet (OC)5Cr=PR, which has a BDEst of 40.5 kcal/mol, the a- and n-components are 62.4 and 40.9 kcal/mol, respectively. 

Energy decomposition based on BLW-ED theory [5]. Average number of molecules able to form H-bonds with the ion considered. 

Glendening, E. D., Streitwieser, A., 1994, Natural Energy Decomposition Analysis An Energy Partitioning Procedure for Molecular Interactions With Apphcation to Weak Hydrogen Bonding, Strong Ionic, and Moderate Donor-Acceptor Interactions , J. Chem. Phys., 100, 2900. 

M2-CO the first adduct bond energies are greater for Co, Ru, Pd, W, Ir, and Pt than V, Fe, Ni, Nb, and Mo. For the trimers, iron has a weaker bond than the other metals studied. For the tetramer and larger clusters the reactivity is controlled by the value of kn and no longer by the competition between uni molecular decomposition and collisional stabilization. The large cluster regime is not covered by this model used to make the correlation between kinetics and energeti cs. 

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