Giant Faraday Rotation in Mesogenic Organic Molecules

Faraday rotation, the rotation of the polarization of light due to a magnetic field in the direction of propagation of the light, is used in applications ranging from quantum memory to the detection of biomagnetic fields. For these applications large Faraday rotation is necessary, but absorption of light is detrimental. In search of these properties, we have characterized the Verdet constant of a so far unexplored class of mesogenic organic molecules. We report their spectra and provide an interpretation. A Verdet constant of almost 2.5 × 105 deg T–1 m–1 is found around 520 nm. This Verdet constant is 3 orders of magnitude larger than the largest known for organic molecules in a region without spectral features. We attribute this enormous Faraday rotation to resonant enhancement by a triplet excitation that does not appear in the linear absorption spectrum and to near-resonant enhancement by low-energy singlet excitations. Furthermore we are able to switch the Faraday rotation by changing the liquid cryst...

[1]  Hans W. Horn,et al.  ELECTRONIC STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS: THE PROGRAM SYSTEM TURBOMOLE , 1989 .

[2]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[3]  Ventsislav K. Valev,et al.  Precise measurements of Faraday rotation using ac magnetic fields , 2008 .

[4]  J. Autschbach,et al.  A gauge‐origin independent expression for the Verdet constant within the time‐dependent density functional theory , 2005 .

[5]  Rajeev J. Ram,et al.  Magneto-optical properties of iron oxide films , 2003 .

[6]  R. Segalman,et al.  Tuning Polythiophene Crystallization through Systematic Side Chain Functionalization , 2010 .

[7]  J. Autschbach,et al.  Calculation of Verdet constants with time-dependent density functional theory: implementation and results for small molecules. , 2005, The Journal of chemical physics.

[8]  Samuel H. Brown,et al.  Spin‐dependent magneto‐optical rotation for free radicals and for singlet–triplet transitions , 1978 .

[9]  K. Clays,et al.  Synthesis, spectroscopy, nonlinear optics, and theoretical investigations of thienylethynyl octopoles with a tunable core. , 2009, Chemistry.

[10]  A. Persoons,et al.  Faraday rotation measurements on thin films of regioregular alkyl-substituted polythiophene derivatives , 2008 .

[11]  Kayoko Miyamoto,et al.  Faraday rotation dispersion measurements of diamagnetic organic liquids and simultaneous determination of natural optical rotatory dispersion using a pulsed magnetic field. , 2013, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[12]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[13]  M. Huang,et al.  Growth and characterization of cerium-substituted yttrium iron garnet single crystals for magneto-optical applications , 2002 .

[14]  M. Frisch,et al.  Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields , 1994 .

[15]  D. Tozer,et al.  Influence of Triplet Instabilities in TDDFT. , 2011, Journal of chemical theory and computation.

[16]  Hitoshi Watarai,et al.  Pulsed magnetic field faraday imaging of diamagnetic liquids. , 2009, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[17]  Valeriy V. Yashchuk,et al.  Sensitive Magnetometry based on Nonlinear Magneto-Optical Rotation , 2000 .

[18]  Sarbani Chakraborty,et al.  Study of magneto-optic element as a displacement sensor , 2011 .

[19]  S. Hattori,et al.  Characteristic of Magnetic Rotation Spectra at Singlet-Triplet Transition Frequencies , 1965 .

[20]  S. Dancoff.  Non-Adiabatic Meson Theory of Nuclear Forces , 1950 .

[21]  Manfred Hammer,et al.  Applications of magneto-optical waveguides in integrated optics: review , 2005 .

[22]  Michael Faraday,et al.  Experimental Researches in Electricity , 1880, Nature.

[23]  P. Hansen,et al.  Magnetic and magneto-optic properties of lead- and bismuth-substituted yttrium iron garnet films , 1983 .

[24]  K. Clays,et al.  All Optical Determination of Microscopic and Macroscopic Structure of Chiral, Polar Microcrystals from Achiral, Nonpolar Molecules , 2012 .

[25]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[26]  E. M. García-Frutos,et al.  Nonlinear optical thin film device from a chiral octopolar phenylacetylene liquid crystal. , 2012, The Journal of organic chemistry.

[27]  Inge Asselberghs,et al.  Liquid crystals from C3-symmetric mesogens for second-order nonlinear optics. , 2006, Angewandte Chemie.

[28]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[29]  B. S. Snowden,et al.  Magnetic rotation spectrum of singlet-triplet transitions: Part II. Pyrazine , 1965 .

[30]  L. R. Dalton,et al.  Organic electro-optic materials , 2004 .

[31]  J. Perdew,et al.  Erratum: Density-functional approximation for the correlation energy of the inhomogeneous electron gas , 1986, Physical review. B, Condensed matter.

[32]  Thierry Verbiest,et al.  Faraday rotation and its dispersion in the visible region for saturated organic liquids. , 2012, Physical chemistry chemical physics : PCCP.

[33]  Antonio Rizzo,et al.  MCSCF calculations of Verdet constants , 1994 .

[34]  O. Sporns,et al.  Complex brain networks: graph theoretical analysis of structural and functional systems , 2009, Nature Reviews Neuroscience.

[35]  Hiroyuki Takeda,et al.  Compact optical one-way waveguide isolators for photonic-band-gap microchips , 2008 .

[36]  W. Eberhardt,et al.  The magnetic rotation spectrum of singlet-triplet transitions , 1961 .

[37]  P. Jørgensen,et al.  Coupled cluster calculations of Verdet constants , 1997 .

[38]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[39]  K. Bohnert,et al.  Optical fiber sensors for the electric power industry , 2005 .

[40]  Benoît Champagne,et al.  A joint theoretical-experimental investigation of the Faraday effect in benzene, toluene, and p-xylene. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[41]  H. Gall,et al.  Temperature dependence of the octahedral and tetrahedral magnetooptical coefficients in YIG , 1972 .

[42]  B. Sanders,et al.  Optical quantum memory , 2009, 1002.4659.