Theoretical study of the large linear dichroism of herapathite

Lei Liang, Paul Rulis, Bart Kahr, W. Y. Ching

Research output: Contribution to journalArticle

Abstract

The remarkable linear dichroism of herapathite (HPT), the active component of polaroid, resisted explanation for more than 150 years because the crystal structure was not solved until very recently. The crystal structure with a formula unit of (C20 H24 N2 O2 H2)4 C2 H4 O2 3SO 4 2I3 6H2 O in an orthorhombic cell has a slight disorder related to the positions of the six water molecules and the acetic-acid molecule. The electronic and optical properties of this complex crystal are here calculated on the basis of the newly described x-ray structure using a density-functional theory based method with local-orbital basis. The theoretical optical spectrum of HPT shows giant optical anisotropy as observed experimentally with an anisotropy factor on the order of 385 that can be ascribed to transitions between molecular levels of the 2 I3- chains that are oriented along the crystalline b axis. It is shown that the key to achieve large anisotropy is to align the iodine ions in a quasi-one-dimensional chain via confinement in a clatharate channel formed by the quinine molecules. The solvent molecules in the crystal have a minimal effect. The implications of this work on biologically relevant systems are discussed.

Original languageEnglish (US)
Article number235132
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume80
Issue number23
DOIs
StatePublished - Dec 30 2009

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics

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