Morokuma-Kitaura energy decomposition

K. Morokuma and K. Kitaura, Energy decomposition analysis of molecular interactions, in P. Politzer,... 

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. 

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 (1982) Energy decomposition analysis of molecular interactions. In Politzer P, Truhlar DG (eds) Chemical applications of atomic and molecular electrostatic potentials. Plenum, New York, pp 215-242... 

The first and very popular energy decomposition scheme that is used to decompose the total INT into various contributing factors was developed by Kitaura and Moroknma in the late 1970s. This method was mainly developed to decompose the INT of hydrogen-bonded systans within the Hartree-Fock approximation. Since then, it has also been successfully applied to donor-acceptor pairs, % and a interactions in transition metal complex, and decomposition of electron density. A broad outline of the key steps involved in the analysis of various components of the INT is provided in the following section. Before we proceed to the KM analysis in detail, it is important to look at the initial decomposition scheme developed by Morokuma. We start the discussion by taking a dimer AB into consideration. 

For Inter Molecular Perturbation Theory (IMPT) see Hayes, I. C. Stone, A. J. An intermolecular perturbation theory for the region of moderate overlap, Mol. Phys. 1984, 53, 83-105 papers of this kind, however, contain a large amount of theoretical and mathematical detail and are not transparent to the uninitiated. For Symmetry-Adapted Perturbation Theory (SAPT) see e.g. Bukowski, R. Szalewicz, K. Chabalovski, C. F. Ab initio interaction potentials for simulations of dinitramine solutions in supercritical carbon dioxide with cosolvents, J. Phys. Chem. 1999, A103, 7322-7340, and references therein. The Morokuma decomposition scheme is described in Kitaura, K. Morokuma, K. A new energy decomposition scheme for molecular interactions within the Hartree-Fock approximation, Int. J. Quantum Chem. 1976,10, 325-340. 

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. 

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 ... 

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