Interaction energy decomposition

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]. 

Using quantum chemical calculations for Monte-Carlo-generated conformers of 

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Keywords Polarizable force fields, Intermolecular interactions, Energy decomposition, Density... 

Sokalski WA, Harlharan PC, Kaufman JJ (1983) A self-consistent field interaction energy decomposition study of 12 hydrogen-bonded dimers. J Chem Phys 87 2803-2810... 

In summary, the MP2 interaction energy decomposition reveals the following terms ... 

Figure 8-3. Variational-perturbational scheme of interaction energy decomposition. The circles denote the consecutive levels of theory while the arrows designate the corresponding correction terms...

To express the collective solvent reaction coordinate as in equation (6), it is necessary to define the specific diabatic potential surface for the reactant and product state. This, however, is not a simple task, and there is no unique way of defining such diabatic states. What is needed is a method that allows the preservation of the formal charges of the fragments of reactant and product resonance states. At the same time, solvent effects can be incorporated into electronic structure calculations in molecular dynamics and Monte Carlo simulations. Recently, we developed a block-localized wave function (BLW) method for studying resonance stabilization, hyperconjugation effects, and interaction energy decomposition of organic molecules.20-23 The BLW method can be formulated to specify the effective VB states.14... 

Sokalski, W. A., Roszak, S., Hariharan, P. C., and Kaufman, J. J. Improved SCF interaction energy decomposition scheme corrected for basis set superposition effect, Int. J. Quantum Chem. 

H-bonds intermolecular H-bonds Tr-electron delocalization topological parameters critical points QTAM (Quantum Theory Atoms in Molecules method) covalent hydrogen bonds interaction energy decomposition scheme. 

Ababou, A., van der Vaart, A., Gogonea, V., Merz Jr., K.M. Interaction energy decomposition in protein-protein association A quantum mechanical study of bamase-barstar complex. Biophys. Chem. 2007,125,221-36. 

The performances of the CP corrections to the interaction energy decomposition can be appreciated in a systematic study on representative hydrogen-bond dimers. A general review on the CP theory has been done by van Dujneveldt et al. (who prefer to use a different decomposition). 

Ionic Clusters with Weakly Interacting Components 191 Table 3. The interaction energy decomposition for the case of GeH3" (H2) . 

The primary interaction energy decomposition is presented in Graph 16.10 for the attractive part of the potential energy surface. 

In addition to the technical aspects related to the size of molecular systems even more serious problem constitutes the elimination of the basis set dependence of components obtained within different interaction energy decompositions. The performance of various decompositions can be examined by comparison of corresponding results with the most accurate and unquestioned values obtained within rigorously defined perturbational approach with basis sets approaching Hartree-Fock limit. Such accurate results obtained within Symmetry Adapted Perturbation Theory (SAPT) are known for the smallest systems only He2 and H20)2 [6]. 

Cumpaiu.on the accuracy of first order electrostatic and exchange terms obtained within various SCF interaction energy decompositions with corresponding SAPT results for the benchmark test case He..He (R--5.6 au). All interaction energy values are given in nH and corresponding errors are calculated in respect to SAPT results (in parentheses). 

Ess DH, Goddard WA, Periana RA. Electrophibc, ambiphibc, and nucleophilic C—H bond activation understanding the electronic continuum of C H bond activation through transition-state and reaction pathway interaction energy decompositions. Organometallics. 2010 29 6459-6472. 

The Pixel intermolecular interaction energy decomposition allows a better understanding of the forces that are at the root of the phenomenon of polymorphism. Moreover, the same quantum chemical calculation (MP2/6-31G ) that provides the electron density for the Pixel calculation also provides total electronic energies and so, in principle, a way of also estimating intramolecular energy differences between polymorphs. 

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