Intermolecular Energy decomposition analyses

Intermolecular Energy decomposition analyses (EDA) are very useful approaches to calibrate force fields. Indeed, an evaluation of the different physical components of the interaction energy, especially of the many-body induction, is a key issue for the development of polarisable models. 

Reinhardt P, Piquemal J-P, Savin A (2008) Fragment-localized Kohn-Sham orbitals via a Singles-CI procedure and application to local properties and intermolecular energy decomposition analysis. J Chem Theory Comput 4 2020... 

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]. 

The density-based energy decomposition analysis (DEDA) method was recently developed by Wu et al. [38] for intermolecular interactions, as illustrated in Fig. 4.1. Similar to other energy decomposition analysis approaches, the determination of binding energy components between two isolated molecules - A (with density po, A) and B (with density po, B) - and their binding complex... 

Mo, Y, Gao, and Peyerimhoff, S. D. Energy decomposition analysis of intermolecular interactions using a block-localized wave function approach. / Chem. Phys., 112, 5530-5538, doi 10.1063/1.481185 (2000). 

Wu, Q., Ayers, P. W, and Zhang, Y. (2009]. Density-based energy decomposition analysis for intermolecular interactions with variationally determined intermediate state energies,/. Chem. Phys. 131,16,164112. 

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. 

A much more sophisticated and thorough analysis of intermolecular interactions is provided by the natural energy decomposition analysis (NEDA) module of the NBO... 

The intramolecular CHA fonnaUsm received no direct numerical applications. However, the application of the same philosophy to the BSSE problem of intermolecular interactions has been found rather useful [1, 3,4], An eneigy decomposition formalism has also been developed [1], in which the different energy components were defined as the expectation values of the corresponding physical terms of the Hamiltonian the analysis of one of them (that of the diatomic electrostatic interactions in a point-charge qjproximation) had led to the definition of the bond order index [5-8], which has been widely applied in studying different chemical problems. 

Types of intermolecular bonds An excellent overview of hydrogen bonds can be found in the article by Buckingham, Del Bene, and McDowell (Buckingham et al. 2008). In the last few years interest has developed in halogen bonded systems. See Bernal-Uruchurtu et al. (2009) for an introduction and an analysis based on a SAPT decomposition of the interaction energy. 

---