Title: Polyatomic molecules in condensed phase: bond order index and solvation energy studied by RISM-SCF theory
Author(s):

	H.Sato (Depament of Molecular Engineering, Kyoto University, Kyoto, 615-8510, Japan) ,
	D.Yokogawa (Depament of Molecular Engineering, Kyoto University, Kyoto, 615-8510, Japan) ,
	S.Sakaki (Depament of Molecular Engineering, Kyoto University, Kyoto, 615-8510, Japan; Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, 606-8103, Japan) ,

The reference interaction site model - self-consistent field (RISM-SCF) theory was applied to a series of polyatomic molecules in aqueous solution, including CH₄, NH₃, H₂O and HF. The bond order index, which characterizes the chemical bond, and its change by the solvation were studied by comparison with a dielectric continuum model. The change in the electronic structure was also associated with the solvation freeenergy.We find that the bond order indexes are not sensitive to the solvation effect even if the charge assigned to the atom is considerably changed. The distortion in the electronic energy is in proportion to the change in the solvation energy, showing that the linear response regime is a good expression of the solvation process examined here, in spite of solving the non-linear RISM-SCF equation.

Key words: RISM-SCF, electronic structure, PCM, bond order index, linear response
PACS: 31.10.+z, 31.15.Ar, 31.15.Ne, 31.70.Dk, 33.15.Fm, 71.15.-m

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