Kitaura-Morokuma decomposition

Despite the fact that the Kitaura Morokuma approach allows insight into the nature of interaction to be obtained, it has also a lot of limitations. One of the most important is that the binding energy and its components are not free of the basis set superposition error [39]. Another variation-perturbation scheme of the decomposition of the interaction energy was previously proposed [40]. The starting wave functions of the subsystems are obtained in this approach in the dimer-centered basis set (DCBS) hence, the following interaction energy components free of BSSE can be obtained ... 

The natural energy decomposition analysis (the keyword is NEDA) of Glendening and Streitwieser provides a more comprehensive picture of the various energy components contributing to intermolecular interactions. The NEDA decomposition mimics in some ways the older Kitaura-Morokuma analysis, but it avoids the use of non-orthogonal (and exclusion principle-violating) wavefiinctions for the two monomers, with the attendant interpretational ambiguities. 

Kitaura K, Morokuma K (1976) A new energy decomposition scheme for molecular interactions within the Hartree-Fock approximation. Int J Quantum Chem 10 325... 

K. Kitaura and K. Morokuma, Int.. Quantum Chem., 10, 325 (1976). A New Energy Decomposition Scheme for Molecular Interactions Within the Hartree-Fock Approximation. 

Morokuma, K. Kitaura, K. Energy Decomposition Analysis of Molecular Interactions in Chemical Applications of Atomic and Molecular Electrostatic Potentials, Politzer, P Ed. Plenum New York, 1981, pp. 215-242. 

Table 1.6 Comparison between Morokuma-Kitaura and natural energy decomposition analysis (NEDA) " . All values in kcal/mol, calculated with 4-3IG basis set. 

We may now introduce a phenomenological partition of W(M/S). The analogy of W(M/S) with the few body intermolecular AE, extensively studied in QM models, could suggest the use of one of the numerous AE decompositions available in literature. In the past we used, with good results, the following partition (Kitaura and Morokuma, 1976) ... 

Decomposition of interaction energies is desired for qualitative chemical analyses of complicated multi-valent interactions in supramolecular aggregates but such a decomposition cannot be uniquely defined within fundamental physical theory. A popular semi-quantitative decomposition method with nice formal features to be mentioned in this context is Weinhold s natural bond orbital (NBO) approach to intermolecular interactions [232, 233]. Comparable is the recently proposed energy decomposition analysis by Mo, Gao and Peyerimhoff [234, 235] which is based on a block-localized wave function. Other energy decomposition schemes proposed are the energy decomposition analysis (EDA) by Kitaura and Morokuma [236] and a similar scheme by Ziegler and Rauk [237]. 

Morokuma K, Kitaura K. Energy decomposition analysis of molecular interactions. In Politzer P, Truhlar DG, eds. Chemical Applications of Atomic and Molecular Electrostatic Potentials. New York Plenum, 1981 215-242. 

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