Electron correlation, intermolecular interaction

Keywords Localization, interpretability, electron correlation, intermolecular interactions... 

The ab initio methods used by most investigators include Hartree-Fock (FFF) and Density Functional Theory (DFT) [6, 7]. An ab initio method typically uses one of many basis sets for the solution of a particular problem. These basis sets are discussed in considerable detail in references [1] and [8]. DFT is based on the proof that the ground state electronic energy is determined completely by the electron density [9]. Thus, there is a direct relationship between electron density and the energy of a system. DFT calculations are extremely popular, as they provide reliable molecular structures and are considerably faster than FFF methods where correlation corrections (MP2) are included. Although intermolecular interactions in ion-pairs are dominated by dispersion interactions, DFT (B3LYP) theory lacks this term [10-14]. FFowever, DFT theory is quite successful in representing molecular structure, which is usually a primary concern. 

The various methods used in quantum chemistry make it possible to compute equilibrium intermolecular distances, to describe intermolecular forces and chemical reactions too. The usual way to calculate these properties is based on the independent particle model this is the Hartree-Fock method. The expansion of one-electron wave-functions (molecular orbitals) in practice requires technical work on computers. It was believed for years and years that ab initio computations will become a routine task even for large molecules. In spite of the enormous increase and development in computer technique, however, this expectation has not been fulfilled. The treatment of large, extended molecular systems still needs special theoretical background. In other words, some approximations should be used in the methods which describe the properties of molecules of large size and/or interacting systems. The further approximations are to be chosen carefully this caution is especially important when going beyond the HF level. The inclusion of the electron correlation in the calculations in a convenient way is still one of the most significant tasks of quantum chemistry. 

The scope of this work is to deal with the possible treatments of electron correlation in a localized representation. Several methods will be discussed in detail elaborated by present authors. Special attention will be payed to the analysis of the transferability of certain correlation energy contributions. The use of their transferability will be discussed for extended systems series of hydrocarbons and polyenes will be investigated. The transferable properties of the contributions to the correlation energy, furthermore, turned out to be useful in the study of weakly interacting intermolecular systems. A detailed description of this procedure will be given in the present work. 

The SCF-MI BSSE free method does not take into account dispersion forces, connected to electronic intermolecular correlation effects. By using the SCF-MI wave function as a starting point, however, a non orthogonal BSSE free Cl procedure can be developed. This approach was applied to compute intermolecular interactions in water dimer and trimer the resulting ab initio values were used to generate a new NCC-like potential (Niesar et al, 1990). Molecular dynamics simulation of liquid water were performed and satisfactory results obtained (Raimondi et al, 1997). 

Interatomic Coulombic decay (ICD) is an electronic decay process that is particularly important for those inner-shell or inner-subshell vacancies that are not energetic enough to give rise to Auger decay. Typical examples include inner-valence-ionized states of rare gas atoms. In isolated systems, such vacancy states are bound to decay radiatively on the nanosecond timescale. A rather different scenario is realized whenever such a low-energy inner-shell-ionized species is let to interact with an environment, for example, in a cluster. In such a case, the existence of the doubly ionized states with positive charges residing on two different cluster units leads to an interatomic (or intermolecular) decay process in which the recombination part of the two-electron transition takes part on one unit, whereas the ionization occurs on another one. ICD [73-75] is mediated by electronic correlation between two atoms (or molecules). In clusters of various sizes and compositions, ICD occurs on the timescale from hundreds of femtoseconds [18] down to several femtoseconds [76-79]. 

The intermolecular electron correlation (the dispersion interaction) was calculated or estimated for some cation-ligand interactions using configuration interaction (Cl) calculations, perturbation theory or on the basis of a statistical model (see Table 4). Its contribution to the total interaction energy is less than 10% throughout. 

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