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J. Chem. Phys. 120, 11557 (2004); http://dx.doi.org/10.1063/1.1753552 (7 pages)

Theory of the two step enantiomeric purification of 1,3 dimethylallene

David Gerbasi1, Paul Brumer1, Ioannis Thanopulos2, Petr Král2, and Moshe Shapiro2

1Chemical Physics Theory Group, Department of Chemistry, The University of Toronto, 80 St. George Street, Toronto, M5S3H6, Canada
2Department of Chemical Physics, The Weizmann Institute of Science, Rehovot, 76100, Israel

(Received 12 November 2003; accepted 1 April 2004)

An application of a recently proposed [P. Král et al., Phys. Rev. Lett. 90, 033001 (2003)] two step optical control scenario to the purification of a racemic mixture of 1,3 dimethylallene is presented. Both steps combine adiabatic and diabatic passage phenomena. In the first step, three laser pulses of mutually perpendicular linear polarizations, applied in a “cyclic adiabatic passage” scheme, are shown to be able to distinguish between the L and D enantiomers due to their difference in matter-radiation phase. In the second step, which immediately follows the first, a sequence of pulses is used to convert one enantiomer to its mirror-imaged form. This scenario, which only negligibly populates the first excited electronic state, proves extremely useful for systems such as dimethylallene, which can suffer losses from dissociation and internal conversion upon electronic excitation. We computationally observe conversion of a racemic mixture of dimethylallene to a sample containing ≈95% of the enantiomer of choice. © 2004 American Institute of Physics.

© 2004 American Institute of Physics

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KEYWORDS and PACS

PACS

  • 82.30.Qt

    Isomerization and rearrangement

  • 82.50.-m

    Photochemistry

  • 33.80.-b

    Photon interactions with molecules

  • 33.15.Hp

    Barrier heights (internal rotation, inversion, rotational isomerism, conformational dynamics)

  • 33.50.Hv

    Radiationless transitions, quenching

ARTICLE DATA

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

For access to fully linked references, you need to log in.
    R. Noyori, in Asymmetric Catalysis in Organic Synthesis (Wiley-Interscience, New York, 1994).

    M. Shapiro, E. Frishman, and P. Brumer, Phys. Rev. Lett. 84, 1669 (2000).

    D. Gerbasi, M. Shapiro, and P. Brumer, J. Chem. Phys. 115, 5349 (2001)JCPSA6000115000012005349000001.

    E. Frishman, M. Shapiro, D. Gerbasi, and P. Brumer, J. Chem. Phys. 119, 7237 (2003)JCPSA6000119000014007237000001.

    P. Král, I. Thanopulos, M. Shapiro, and D. Cohen, Phys. Rev. Lett. 90, 033001 (2003).

    P. Král and M. Shapiro, Phys. Rev. Lett. 87, 183002 (2001).

    P. Král, Z. Amitay, and M. Shapiro, Phys. Rev. Lett. 89, 063002 (2002).

    D. T. Colbert and W. H. Miller, J. Chem. Phys. 96, 1982 (1992)JCPSA6000096000003001982000001.


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