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Research Article

Chiral heliconical ground state of nanoscale pitch in a nematic liquid crystal of achiral molecular dimers

Dong Chen, Jan H. Porada, Justin B. Hooper, Arthur Klittnick, Yongqiang Shen, Michael R. Tuchband, Eva Korblova, Dmitry Bedrov, David M. Walba, Matthew A. Glaser, Joseph E. Maclennan, and Noel A. Clark
PNAS October 1, 2013 110 (40) 15931-15936; https://doi.org/10.1073/pnas.1314654110
Dong Chen
aDepartment of Physics and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0390;
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Jan H. Porada
bDepartment of Chemistry and Biochemistry and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0215;
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Justin B. Hooper
cDepartment of Materials Science and Engineering, The University of Utah, Salt Lake City, UT 84112; and
dLiquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0390
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Arthur Klittnick
aDepartment of Physics and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0390;
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Yongqiang Shen
aDepartment of Physics and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0390;
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Michael R. Tuchband
aDepartment of Physics and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0390;
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Eva Korblova
bDepartment of Chemistry and Biochemistry and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0215;
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Dmitry Bedrov
cDepartment of Materials Science and Engineering, The University of Utah, Salt Lake City, UT 84112; and
dLiquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0390
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David M. Walba
bDepartment of Chemistry and Biochemistry and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0215;
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Matthew A. Glaser
aDepartment of Physics and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0390;
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Joseph E. Maclennan
aDepartment of Physics and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0390;
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Noel A. Clark
aDepartment of Physics and Liquid Crystal Materials Research Center, University of Colorado Boulder, Boulder, CO 80309-0390;
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  • For correspondence: noel.clark@colorado.edu
  1. Contributed by Noel A. Clark, August 8, 2013 (sent for review July 10, 2013)

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  • Twist–bend nematic phase of achiral dimers
    - Sep 19, 2013
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Significance

The appearance of new nematic liquid crystal (LC) equilibrium symmetry (ground state) is a rare and typically important event. The first and second nematics were the helical phase and blue phase of chiral molecules, both found in 1886 in cholesteryl benzoate by Reinitzer, discoveries that marked the birth of LC science. The third nematic, the achiral uniaxial phase, also found in the 19th century, ultimately formed the basis of LC display technology and the portable computing revolution of the 20th century. Despite this achievement, the 20th can claim only the fourth nematic, the lyotropic biaxial phases found by Saupe. Now, early in the 21st, the heliconical structure of the fifth nematic is observed, an exotic chiral helix from achiral molecules.

Abstract

Freeze-fracture transmission electron microscopy study of the nanoscale structure of the so-called “twist–bend” nematic phase of the cyanobiphenyl (CB) dimer molecule CB(CH2)7CB reveals stripe-textured fracture planes that indicate fluid layers periodically arrayed in the bulk with a spacing of d ∼ 8.3 nm. Fluidity and a rigorously maintained spacing result in long-range-ordered 3D focal conic domains. Absence of a lamellar X-ray reflection at wavevector q ∼ 2π/d or its harmonics in synchrotron-based scattering experiments indicates that this periodic structure is achieved with no detectable associated modulation of the electron density, and thus has nematic rather than smectic molecular ordering. A search for periodic ordering with d ∼ in CB(CH2)7CB using atomistic molecular dynamic computer simulation yields an equilibrium heliconical ground state, exhibiting nematic twist and bend, of the sort first proposed by Meyer, and envisioned in systems of bent molecules by Dozov and Memmer. We measure the director cone angle to be θTB ∼ 25° and the full pitch of the director helix to be pTB ∼ 8.3 nm, a very small value indicating the strong coupling of molecular bend to director bend.

Footnotes

  • ↵1To whom correspondence should be addressed. E-mail: noel.clark{at}colorado.edu.
  • Author contributions: D.C., J.H.P., J.B.H., A.K., Y.S., M.R.T., E.K., D.B., D.M.W., M.A.G., and N.A.C. designed research; D.C., J.H.P., J.B.H., A.K., Y.S., M.R.T., E.K., M.A.G., and N.A.C. performed research; J.H.P. and E.K. contributed new reagents/analytic tools; D.C., J.H.P., J.B.H., A.K., Y.S., M.R.T., D.B., D.M.W., M.A.G., J.E.M., and N.A.C. analyzed data; and D.C., J.H.P., D.B., J.E.M., and N.A.C. wrote the paper.

  • The authors declare no conflict of interest.

  • See Commentary on page 15855.

  • This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1314654110/-/DCSupplemental.

Freely available online through the PNAS open access option.

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Heliconical nematic liquid crystal
Dong Chen, Jan H. Porada, Justin B. Hooper, Arthur Klittnick, Yongqiang Shen, Michael R. Tuchband, Eva Korblova, Dmitry Bedrov, David M. Walba, Matthew A. Glaser, Joseph E. Maclennan, Noel A. Clark
Proceedings of the National Academy of Sciences Oct 2013, 110 (40) 15931-15936; DOI: 10.1073/pnas.1314654110

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Heliconical nematic liquid crystal
Dong Chen, Jan H. Porada, Justin B. Hooper, Arthur Klittnick, Yongqiang Shen, Michael R. Tuchband, Eva Korblova, Dmitry Bedrov, David M. Walba, Matthew A. Glaser, Joseph E. Maclennan, Noel A. Clark
Proceedings of the National Academy of Sciences Oct 2013, 110 (40) 15931-15936; DOI: 10.1073/pnas.1314654110
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