Electronic structure and chemical reaction in solution

Department of Molecular Engineering Kyoto University hirofumi moleng, kyoto-u.ac.jp 

Keywords Electronic Structure in Solution, Chemical Reactions, RISM-SCF/MCSCF 

The ab initio approach of molecular dynamics (MD), which was originated by Car and Parrinello, or combined methods of standard MO theory and molecular simulation are the most straightforward realization of such couplings. However, the treatment has serious limitations or difficulties in terms of system size it will be virtually impossible to treat even a small system of a size typical of classical molecular simula- 

The continuum model, in which solvent is regarded as a dielectric continuum, has been used for a long time to study solvent effects [2]. Solvation energies can be primarily approximated by a reaction field owed to polarization of the dielectric continuum as solvent, and other contributions such as dispersion interactions, which must be explicitly considered for non-polar solvent systems, have usually been treated with an empirical quantity such as the macroscopic surface tension of the solvent. An obvious advantage of the method is its handiness, whilst its disadvantage is an artifact introduced at the boundary between the solute and solvent. Agreement between experiment and theory is considerably governed by the boundary conditions. 

The RISM-SCF/MCSCF [4] which will be elucidated in this chapter is the third method that overcomes above mentioned difficulties. The method combines the two theoretical elements the ab initio MO method (quantum chemistry) and the RISM (statistical mechanics of liquids), and elicits the nature of chemical system in solution with a moderate computational demanding. 

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Molecular Theory of Solvation, ed. F. Hirata in Understanding Chemical Reactivity, Vol. 24, Kluwer Academic Publishers, 2003 R 218 H. Sato, Electronic Structure and Chemical Reaction in Solution , p. 61... 

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