Exciton Coupling Theory of Circular Dichromism Spectra .

1. Qualitative Analysis of Circular Dichroism Spectrum Peking University Jian Deng 2007.05.31

3. Energy Splitting Why is energy splitting more easily observable in CD Spectrum ?

4. X* Y* V XY 0 0 a a X Y Ground State Excited State Local Excitation Local excitation Delocalized Excitaion Exciton X* Y*

6. Dipole Moment small Permanent dipole moment of groud state Permanent dipole moment of excited state Electric transition moment

7. Exciton Coupling Theory 1 2 3 4

8. V XY 0 0 a a X Y Local Excitation Local excitation Delocalized Excitaion Exciton Local Excitation Local excitation Delocalized Excitaion Exciton V XY 0 0 a a X Y Degenerate Near-degenerate

10. Polarization Direction of Chromophore 1 B b (220 nm) 1 L b (310 nm) 1 L a (285 nm)

11. 260 nm

12. (R)-BEBPB (R)-CBEBPB (R)-BEBPB1r (R)-BEBPB2r (R)-CBEBPB1r (R)-CBEBPB2r Conformational Analysis

13. 1 Guess of initial conformation R-BEBPM

14. A simple optimazaition

15. 2 Rotation of Dihedral Angles

16. 3 Geometric Optimization of PM3 PM3 Name D7-8-21-22 D8-21-22-23 D21-22-23-27 D4-7-11-12 25-26-28-33 30-31-40-45 Energy(au) 1 -110 -171 168 -98 100 47 1.5288 1a -110 -171 168 -98 100 47 1.5288 1b -100 -87 -158 -93 75 47 1.5257 10 -118 -95 -173 -97 83 47 1.5229 1100 -118 -95 -173 -97 83 47 1.5229 10a -77 -69 -77 -87 82 47 1.5225 11a 113 177 -64 -94 87 47 1.5369 110 -146 76 169 -101 106 47 1.5261 1111 -150 81 162 -102 101 47 1.5234 110a 131 94 68 -100 102 47 1.5296 111 -110 -171 169 -98 100 47 1.5288 111b -111 -172 169 -98 100 47 1.5288 1110 -129 -111 146 -97 111 47 1.528 1111a -152 76 121 -107 71 47 1.5258 1110a -98 -72 -130 -95 70 47 1.5263 111a 11 -77 -69 -77 -87 82 0 1.5218

17. 3 Geometric Optimization of HF/3-21G HF/3-21G Name D7-8-21-22 D8-21-22-23 D21-22-23-27 D4-7-11-12 25-26-28-33 30-31-40-45 Energy Dipole 124.fchk -105 145 177 -96 91 60 -2120.948 7.4666 1a -105 145 177 -96 91 60 -2120.948 7.466 1b -105.51 144.91 176.74 -96.07 1.11 60.29 -2120.948 7.4622 10 -105 145 177 -96 91 60 -2120.948 7.4663 111 -105 145 177 -96 91 60 -2120.948 7.4652 110 -105 145 177 -96 91 60 -2120.948 7.3908 1110 -105 145 177 -96 91 60 -2120.948 7.4582 1111a -105 145 177 -96 91 60 -2120.948 7.4662 10a -58 -74 -74 -81 35 60 -2120.944 30.582 11a 124 -173 -68 -110 72 60 -2120.95 6.2576 110a 146 106 71 -105 138 60 -2120.945 8.858

18. 1111a 110 10 1b

19. 4 Geometric Optimization of B3LYP/6-31G*

21. R-CBEBPB

24. Analysis of CD with Exciton Coupling Theory

27. R-CBEBPB R-BEBPB ORD Calculated from Experimental Rotational Strength

28. Plans 1 Synthesis and Characterization of Chiral Polymers Containing Viologen 2 Calculation of the polarization derection 3 Plan to write my paper