1. Energy and Electron Transfer MMP+ discussion Chapter 7 first half December 17, 2002 Zhiqiang Liu

2. Transfer

3. Competing Processes upon encountering

4. Trivial Mechanism for energy transfer

5. Spectral Overlap Integral

6. Trivial Mechanism for electron transfer http://chemed.chem.purdue.edu/demos/main_pages/9.4.html

7. Non-trivial energy transfer

8. Forster Theory of Coulombic Energy Transfer  2 : orientation. Alignment factor J: overlap. Energy match of donor and acceptor R: distance between dipoles dipole-dipole interaction

9. Energy transfer by electron exchange Dexter:

10. Comparison: Forster v. Dexter Dexter: Forster: 1.Dependence on separation. Dexter much stronger than Forster. 2.Forster depends on oscillator strength. 3.Both dependent on J. 4.Dexter involves excited states

11. Generating D and A*

12. Triplet Triplet Annihilation. Energy transfer via electron exchange

13. Electron Transfer

14. Excited states: better oxidizing and reducing agents

15. Free energy for gas phase electron transfer

16. Free energy in solution phase GG Gas phase results + terms for solution Electrochemical potential in solution

17. Coulombic term in free energy of electron transfer

18. Libby vs. Marcus theory Three events: 1.Electron transfer 2.Molecular reorientation 3.Solvent reorientation Libby: Molecular and solvent after Electron. Marcus: Assumptions: 1. Loose bonding between molecules for classical phys/chem analysis 2. Geometrical and solvent reorientation to provide energy for the e jump Frank-Condon e Jump

19. Libby vs. Marcus theory

20. Marcus for non zero free energy difference

21. Experimental evidence for Marcus Inverted Region