Chemical Physics Letters, Vol.361, No.1-2, 106-114, 2002
Density functional theory study on the geometric, electronic and vibrational structures of alkali metal porphyrin complexes
The ground-state geometry, electronic structures and vibrational frequencies of alkali metal porphyrin complexes, M2P (M = Li, Na, K), have been studied using B3LYP/6-31G(d) method. The computed structures were compared with the crystallographic data of related compounds. TheNa(2)P and K2P molecules have D-4h symmetry with the two alkali metal atoms locating on the different sides of the porphyrin plane. For Li2P, the energy of D-4h structure is higher than the symmetry broken C-2h structure, but the energy difference is very small. Natural population analysis suggests a significant charge transfer from the alkali metals to the porphyrin ring. The vibrational frequencies of M2P (M = Li, Na, K) were calculated and the results were compared with zinc porphyrin (ZnP). (C) 2002 Elsevier Science B.V. All rights reserved.