Comprehensive SPHYB and B3LYP-DFT Studies of Two Types of Ferrocene

Abstract

Structural and optoelectronic properties of ferrocene (FeC10H10) using various exchange correlation potentials including Spin Polarized Generalized Gradient Approximation (SPGGA), Hybrid Density Functional Theory (SPHYB‐DFT), and hybrid density functional Becke3LYP are investigated. Obtained bandgap by the SPHYB‐DFT and SPGGA methods show consistency with the experiment, that are indirect and direct, respectively. The cell size effects on physical properties of ferrocene studied about two types of its lattice parameters (I and II). The calculated results reveal that the cell size and the lattice parameters have a remarkable effect on optoelectronic and magnetic properties of ferrocene. However, there is no significant difference between I and II within molecular, structural and charge transitions in calculating UV/Vis spectrum. The calculated electronic absorption spectrum is in good agreement with experiment, in which two major electron‐transition bands derived from d–d (n → n*) and n → π* metal to ligand. NBO analyses show that there are strong donor‐acceptor interactions between central Fe atoms and cyclopentadienyl (Cp) rings that these results are in close agreement with contour plots of charge densities for prediction of the strong covalent bond between C and Fe. The optoelectronic properties of ferrocene predict that it can be efficiently used in the semiconductor devices.

Antioxidant and Anticancer Properties of Functionalized Ferrocene with Hydroxycinnamate Derivatives—An Integrated Experimental and Theoretical Study

“…For Fc complexes, the HOMO is concentrated only on the ferrocenyl moiety while the LUMO is more equally distributed in the whole molecule. This is in agreement with previous calculations. ,, ESP maps show that the most negative part is located mostly on the CO bond for all compounds, while the most positive part is found on the O–H sites. In case of Fc complexes, the positive charges are also found on the ferrocenyl moieties.…”

“…In the complex structures, the ligands are similarly presented and the cyclopentadienyl rings make an angle of 86–87° versus the phenyl ring of the ligands through the dihedral C12–N–C cp –C cp . The ferrocenyl moieties are in the eclipse form with a Fe–C distance of about 2.11–2.13 Å, which is in agreement with analogous ferrocenes. , The optimized geometries, HOMO, LUMO, and ESP maps of all compounds are presented in Figure S11. Principal coordination parameters of all structures are reported in Table S1.…”

“…This is in agreement with previous calculations. 16,93,94 ESP maps show that the most negative part is located mostly on the CO bond for all compounds, while the most positive part is found on the O−H sites. In case of Fc complexes, the positive charges are also found on the ferrocenyl moieties.…”

“…The ferrocenyl moieties are in the eclipse form with a Fe−C distance of about 2.11−2.13 Å, which is in agreement with analogous ferrocenes. 93,94 The optimized geometries, HOMO, LUMO, and ESP maps of all compounds are presented in Figure S11. Principal coordination parameters of all structures are reported in Table S1.…”

Polar Metallocenes

“…Density functional theory gives reasonable geometries for metallocene molecules [24,25,26]. Xu et al [27] compared several gradient-corrected functionals, as well as the local density approximation (LDA), and found that the B3LYP functional gives the best agreement between the experimental and theoretical molecular geometry.…”