Author: Basiuk, Vladimir A.

Source: Journal of Computational and Theoretical Nanoscience, Volume 2, Number 3, September 2005 , pp. 370-377(8)

Publisher: American Scientific Publishers

Abstract:

We performed DFT calculations (at the B3LYP/LANL2MB theoretical level, implemented in Gaussian 03W) for the interaction of free porphine ligand and a number of its metal complexes with C₆₀ molecule, in order to analyze how the nature of central metal ion influences the geometry and electronic characteristics. The results were compared to our BLYP/DN (DMol3 implementation) results reported earlier. The Gaussian calculations turned to be not only less efficient in terms of time, but also failed to optimize the geometry of Mn(II)-containing systems. The interaction strength remains to be a function of the central atom, however the interaction of H₂P with C₆₀ is not weaker as compared to the metal complexes. Similarly to the BLYP/DN results, in most porphine—C₆₀ complexes, two closest contacts of metal are those with carbon atoms of (6, 6) bond. There are three exceptions in the present case, versus only one (VOP · C₆₀) in the previous study: the closest M-C contacts involve (5, 6) bond in H₂P · C₆₀ and VOP · C₆₀, and in PdP · C₆₀, Pd ion coordinates to the six-membered ring. The interaction with C₆₀ influences the porphine geometry, and its change depends on the central atom. The most striking feature (apparently an artifact) was found for H₂P · C₆₀, where H₂P molecule stretches along the axis connecting two opposite meso-C atoms and shrinks in the perpendicular direction. The central metal ions interact stronger with C₆₀ than the atoms belonging to the porphine ligand do. As a result, in all complexes except for VOP · C₆₀ and MnClP · C₆₀, the metal is located between the macrocyclic plane and C₆₀. The changes in electrostatic potential and spin density distribution, HOMO and LUMO shape are discussed as well.

Keywords: PORPHINE; METAL PORPHINATES; FULLERENE C60; DFT; GEOMETRY; ELECTRONIC STRUCTURE

Document Type: Research article

DOI: http://dx.doi.org/10.1166/jctn.2005.206

Publication date: 2005-09-01

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