Ab Initio Quantum Chemical Study of Electron Transfer in Carboranes
Abstract
The electron transfer (ET) properties of 10- and 12-vertex carboranes are investigated by the ab initio Hartree-Fock method within the Marcus-Hush (MH) two-state model and the Koopman theorem (KT) approach. The calculated value of the ET coupling matrix element, V(subAB), is consistently higher in the KT approach than in the MH two-state model. For the carborane molecules functionalized by -CH(sub2) groups at C-vertices, V(subAB) strongly depends on the relative orientation of the planes containing the terminal -CH(sub2) groups. The predicted conformation dependence of V(subAB) offers a molecular mechanism to control ET between two active centers in molecular systems.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 2005
- Accession Number
- ADA440631
Entities
People
- Andrew C. Pineda
- Ranjit Pati
- Ravindra Pandey
- Shashi P Karna
Organizations
- Michigan Technological University