Abstract
Density functional theory (DFT) calculations on the MnIV7O14 and MnIII/MnIV mixed valent Mn7O14- clusters are reported and used to characterize the Mn−O bonding in LixMn2O4 spinel. A recipe is proposed of how to extract from calculations on clusters electronic hopping and charge transfer (CT) energy parameters and to use them in a semiempirical (Hubbard type) Hamitonian which simultaneously accounts for electronic correlation and translational symmetry. The first application of this approach to Mn2O4 shows that, in contrast with conventional band calculations, the 3d electrons of Mn are rather localized. Vibronic coupling due to the 2t2g32eg1 configuration of MnIII with the α1g and the Jahn−Teller(JT) active eg modes is analyzed using DFT calculations of the mixed valent Mn7O14- cluster and is found to lead to a lengthening of the Mn−O bond and to tetragonally elongated octahedra accompanied by an appreciable stabilization energy(−0.445 eV). Vibronic coupling and electron hopping energies obtained from th...
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.