Kitaura-Morokuma approach

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 ... 

There are several variants of the same basic approach which is based on the calculation of some intermediate energies. We shall summarize here the Kitaura-Morokuma [11] version of the method which is the most popular. 

To better describe the nature of the considered hydrogen or DHB, it is useful to decompose the interaction energy into various components. According to the approach of Kitaura and Morokuma, the SCF interaction energy (A SCF) may be decomposed into the following energy terms [19]. 

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. Variational approach (SCF ab-initio calculations) to the study of molecular interactions the origin of molecular interactions. In Ratajczak H, Orville-Thomas WJ, eds. Molecular Interactions. New York Wiley, 1980 21-87. 

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