1. The Effect of the π-Electron
Delocalization Curvature on the
Two-Photon Circular Dichroism of
Molecules with Axial Chirality
Carlos Diaz,† Na Lin,‡,§ Carlos Toro,† Remy
Passier,† Antonio Rizzo,∥ and Florencio E.
ndez†,⊥
† Department of Chemistry, University of Central Florida
‡ State Key Laboratory of Crystal Materials, Shandong University, China
§Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway
∥ Consiglio Nazionale delle Ricerche, Istituto per i Processi Chimico Fisici, Italy
⊥The College of Optics and Photonics, CREOL University of Central Florida
J. Phys. Chem. Lett. 2012, 3, 1808-1813 1

2. Motivation
The understanding of chiral molecules
with major relevance in
biology, pharmacology, catalysis, nanote
chnology, optics and photonics.
Limitations of ECD:
• Dark in the far UV.
Advantages of TPCD:
• Allows access into an unexplored
spectral UV region.
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3. Theoretical-Experimental Approach
TPCD was theoretically TPCD was revisited and
predicted in 1975. expanded in 2006.
Double L-scan Technique
J. Chem. Phys. 1975, 62, 1006. //J. Chem. Phys. 1975, 63, 1348. Opt. Lett. 2008, 33, 2958.
J. Chem.Phys., 2006 , 125, 064113. Chem. Eur. J. 2010, 16, 3504
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4. Definition of TPCD
2
TPCD L R 4 2 g 2 NA TPCD
2 2 3 2
R0 f 0f
15 c0 4 0
1
TPCD TI TI TI
R 0f 0f bB
1 1 0f bB2 2 0f bB 3 3 0f
1
B1TI 0f 3
M p ,0 f 0f P p*,0 f 0f
1
TI
B2 0f 3
T ,0 f
0f P p*,0 f 0f 2
2
TI 1
B3 0f 3
M p ,0 f 0f P p*,0 f 0f
J. Chem. Phys. 1975, 62, 1006. //J. Chem. Phys. 1975, 63, 1348.
J. Chem.Phys., 2006 , 125, 064113.
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5. S-BINOL, S-VANOL and S-VAPOL
( -electron delocalization direction)
TPCD was measured on these three compounds to understand the effect of
conjugation direction and extension.
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6. Two-Photon Absorption (TPA) and
TPCD spectra
S-BINOL
S-VANOL
S-VAPOL
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7. Contributions to RTPCD from the
different transition moments
Electric transition quadrupole
moment contributions
Magnetic transition dipole
moment contributions
J.C.S. Faraday II, 1980, 76, 1249.
Phys. Rev. A 2007, 75, 032518.
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8. F. E. Hernandez A. Rizzo
C. Diaz N. Lin
C. Toro R. Passier
Grant Number CHE-0832622
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