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Large Molecular Third-Order Optical Nonlinearities in Polarized Carotenoids

Marder, Seth R. and Torruellas, William E. and Blanchard-Desce, Mirelle and Ricci, Vincent and Stegeman, George I. and Gilmour, Sharon and Brédas, Jean-Luc and Li, Jun and Bublitz, Greg U. and Boxer, Steve G. (1997) Large Molecular Third-Order Optical Nonlinearities in Polarized Carotenoids. Science, 276 (5316). pp. 1233-1236. ISSN 0036-8075. doi:10.1126/science.276.5316.1233.

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Garito and co-workers have suggested a mechanism to dramatically increase the second hyperpolarizability, γ, in linear π-electron–conjugated molecules. Polarization is introduced that leads to a difference between the dipole moments of the molecule’s ground state and excited state. Here a series of carotenoids was examined that had increasing intramolecular charge transfer (ICT) from the polyenic chain to the acceptor moiety in the ground state, and γ was measured for these compounds as a function of wavelength by third-harmonic generation. The compound with the greatest ICT exhibited a 35-fold enhancement of γ_(max)(the γ measured at the peak of the three-photon resonance) relative to the symmetric molecule β-carotene, which itself has one of the largest third-order nonlinearities known. Stark spectroscopic measurements revealed the existence of a large difference dipole moment, Δμ, between the ground and excited state. Quantum-chemical calculations underline the importance of interactions involving states with large Δμ.

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Additional Information:© 1997 American Association for the Advancement of Science. 22 January 1997; Accepted 7 April 1997. This work was supported by the Air Force Office of Scientific Research, the National Science Foundation Chemistry Division (S.G.B.), the Division of Materials Research (S.R.M.), and the Beckman Institute. The research described in this report was performed in part at the Jet Propulsion Laboratory, California Institute of Technology, as part of its Center for Space Microelectronics Technology and was supported by the Ballistic Missiles Defense Initiative Organization, Innovative Science and Technology Office, through a contract with NASA. The work at Mons, Belgium, is carried out within the framework of the Belgium Prime Minister Office of Science Policy “Poˆ le d’Attraction Interuniversitaire en Chimie Supramole´ culaire et Catalyse” and was supported in part by the Belgium National Fund for Scientific Research and by IBM–Belgium Academic Joint Study. We thank F. Hoffman– LaRoche Ltd. for a generous sample of b-apocarotenal and G. Zerbi and M. Barzoukas for helpful discussions.
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Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Ballistic Missiles Defense Initiative OrganizationUNSPECIFIED
Belgium National Fund for Scientific Research (FNRS-FRFC)UNSPECIFIED
IBM–Belgium Academic Joint StudyUNSPECIFIED
Issue or Number:5316
Record Number:CaltechAUTHORS:20141203-121146482
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Official Citation:Marder, S. R., Torruellas, W. E., Blanchard-Desce, M., Ricci, V., Stegeman, G. I., Gilmour, S., . . . Boxer, S. G. (1997). Large Molecular Third-Order Optical Nonlinearities in Polarized Carotenoids. Science, 276(5316), 1233-1236. doi: 10.1126/science.276.5316.1233
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52334
Deposited On:03 Dec 2014 21:02
Last Modified:10 Nov 2021 19:24

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