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Chiral molecules split light: Reflection and refraction in a chiral liquid

Ghosh, A., Fischer, P.

PHYSICAL REVIEW LETTERS, 97(17), 2006, Featured highlight ‘Fundamental optical physics: Refraction’ Nature Photonics, Nov. 2006. (article)

Abstract
A light beam changes direction as it enters a liquid at an angle from another medium, such as air. Should the liquid contain molecules that lack mirror symmetry, then it has been predicted by Fresnel that the light beam will not only change direction, but will actually split into two separate beams with a small difference in the respective angles of refraction. Here we report the observation of this phenomenon. We also demonstrate that the angle of reflection does not equal the angle of incidence in a chiral medium. Unlike conventional optical rotation, which depends on the path-length through the sample, the reported reflection and refraction phenomena arise within a few wavelengths at the interface and thereby suggest a new approach to polarimetry that can be used in microfluidic volumes.

Featured highlight ‘Fundamental optical physics: Refraction’ Nature Photonics, Nov. 2006.

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DOI [BibTex]

DOI [BibTex]


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Direct chiral discrimination in NMR spectroscopy

Buckingham, A., Fischer, P.

CHEMICAL PHYSICS, 324(1):111-116, 2006 (article)

Abstract
Conventional nuclear magnetic resonance spectroscopy is unable to distinguish between the two mirror-image forms (enantiomers) of a chiral molecule. This is because the NMR spectrum is determined by the chemical shifts and spin-spin coupling constants which - in the absence of a chiral solvent - are identical for the two enantiomers. We discuss how chirality may nevertheless be directly detected in liquid-state NMR spectroscopy: In a chiral molecule, the rotating nuclear magnetic moment induces an electric dipole moment in the direction perpendicular to itself and to the permanent magnetic field of the spectrometer. We present computations of the precessing electric polarization following a pi/2 pulse. Our estimates indicate that the electric polarization should be detectable in favourable cases. We also predict that application of an electrostatic field induces a chirally sensitive magnetization oscillating in the direction of the permanent magnetic field. We show that the electric-field-perturbed chemical shift tensor, the nuclear magnetic shielding polarizability, underlies these chiral NMR effects. (c) 2005 Elsevier B.V. All rights reserved.

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DOI [BibTex]

DOI [BibTex]


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NONLINEAR OPTICAL PROPERTIES OF CHIRAL LIQUIDS Electric-dipolar pseudoscalars in nonlinear optics

Fischer, P., Champagne, B.

In NON-LINEAR OPTICAL PROPERTIES OF MATTER: FROM MOLECULES TO CONDENSED PHASES, 1, pages: 359-381, Challenges and Advances in Computational Chemistry and Physics, 2006 (incollection)

Abstract
We give all overview of linear and nonlinear optical processes that can be specific to chiral molecules in isotropic media. Specifically, we discuss the pseudoscalars that underlie nonlinear optical activity and chiral frequency conversion processes in fluids. We show that nonlinear optical techniques open entirely new ways of exploring chirality: Sum-frequency-generation (SFG) at second-order and BioCARS at fourth-order arise in the electric-dipole approximation and do not require circularly polarized light to detect chiral molecules in solution. Here the frequency conversion in itself is a measure of chirality. This is in contrast to natural optical activity phenomena which are based on the interference of radiation from induced oscillating electric and magnetic dipoles, and which are observed as a differential response to right and left circularly polarized light. We give examples from our SFG experiments in optically active solutions and show how the application of an additional static electric field to sum-frequency generation allows the absolute configuration of the chiral solute to be determined via all electric-dipolar process. Results from ab initio calculations of the SFG pseudoscalar are presented for a number of chiral molecules

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[BibTex]

[BibTex]


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Ring-resonator-based frequency-domain optical activity measurements of a chiral liquid

Vollmer, F., Fischer, P.

OPTICS LETTERS, 31(4):453-455, 2006 (article)

Abstract
Chiral liquids rotate the plane of polarization of linearly polarized light and are therefore optically active. Here we show that optical rotation can be observed in the frequency domain. A chiral liquid introduced in a fiber-loop ring resonator that supports left and right circularly polarized modes gives rise to relative frequency shifts that are a direct measure of the liquid's circular birefringence and hence of its optical activity. The effect is in principle not diminished if the circumference of the ring is reduced. The technique is similarly applicable to refractive index and linear birefringence measurements. (c) 2006 Optical Society of America.

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DOI [BibTex]


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Sign of the refractive index in a gain medium with negative permittivity and permeability

Chen, Y., Fischer, P., Wise, F.

JOURNAL OF THE OPTICAL SOCIETY OF AMERICA B-OPTICAL PHYSICS, 23(1):45-50, 2006 (article)

Abstract
We show how the sign of the refractive index in any medium may be derived using a rigorous analysis based on Einstein causality. In particular, we consider left-handed materials, i.e., media that have negative permittivities and permeabilities at the frequency of interest. We find that the consideration of gain in such media can give rise to a positive refractive index. (c) 2006 Optical Society of America.

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DOI [BibTex]

DOI [BibTex]


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Dynamic Hebbian learning in adaptive frequency oscillators

Righetti, L., Buchli, J., Ijspeert, A.

Physica D: Nonlinear Phenomena, 216(2):269-281, 2006 (article)

Abstract
Nonlinear oscillators are widely used in biology, physics and engineering for modeling and control. They are interesting because of their synchronization properties when coupled to other dynamical systems. In this paper, we propose a learning rule for oscillators which adapts their frequency to the frequency of any periodic or pseudo-periodic input signal. Learning is done in a dynamic way: it is part of the dynamical system and not an offline process. An interesting property of our model is that it is easily generalizable to a large class of oscillators, from phase oscillators to relaxation oscillators and strange attractors with a generic learning rule. One major feature of our learning rule is that the oscillators constructed can adapt their frequency without any signal processing or the need to specify a time window or similar free parameters. All the processing is embedded in the dynamics of the adaptive oscillator. The convergence of the learning is proved for the Hopf oscillator, then numerical experiments are carried out to explore the learning capabilities of the system. Finally, we generalize the learning rule to non-harmonic oscillators like relaxation oscillators and strange attractors.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Movement generation using dynamical systems : a humanoid robot performing a drumming task

Degallier, S., Santos, C. P., Righetti, L., Ijspeert, A.

In 2006 6th IEEE-RAS International Conference on Humanoid Robots, pages: 512-517, IEEE, Genova, Italy, 2006 (inproceedings)

Abstract
The online generation of trajectories in humanoid robots remains a difficult problem. In this contribution, we present a system that allows the superposition, and the switch between, discrete and rhythmic movements. Our approach uses nonlinear dynamical systems for generating trajectories online and in real time. Our goal is to make use of attractor properties of dynamical systems in order to provide robustness against small perturbations and to enable online modulation of the trajectories. The system is demonstrated on a humanoid robot performing a drumming task.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Engineering Entrainment and Adaptation in Limit Cycle Systems – From biological inspiration to applications in robotics

Buchli, J., Righetti, L., Ijspeert, A.

Biological Cybernetics, 95(6):645-664, December 2006 (article)

Abstract
Periodic behavior is key to life and is observed in multiple instances and at multiple time scales in our metabolism, our natural environment, and our engineered environment. A natural way of modeling or generating periodic behavior is done by using oscillators, i.e., dynamical systems that exhibit limit cycle behavior. While there is extensive literature on methods to analyze such dynamical systems, much less work has been done on methods to synthesize an oscillator to exhibit some specific desired characteristics. The goal of this article is twofold: (1) to provide a framework for characterizing and designing oscillators and (2) to review how classes of well-known oscillators can be understood and related to this framework. The basis of the framework is to characterize oscillators in terms of their fundamental temporal and spatial behavior and in terms of properties that these two behaviors can be designed to exhibit. This focus on fundamental properties is important because it allows us to systematically compare a large variety of oscillators that might at first sight appear very different from each other. We identify several specifications that are useful for design, such as frequency-locking behavior, phase-locking behavior, and specific output signal shape. We also identify two classes of design methods by which these specifications can be met, namely offline methods and online methods. By relating these specifications to our framework and by presenting several examples of how oscillators have been designed in the literature, this article provides a useful methodology and toolbox for designing oscillators for a wide range of purposes. In particular, the focus on synthesis of limit cycle dynamical systems should be useful both for engineering and for computational modeling of physical or biological phenomena.

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link (url) DOI [BibTex]


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Design methodologies for central pattern generators: an application to crawling humanoids

Righetti, L., Ijspeert, A.

In Proceedings of Robotics: Science and Systems, Philadelphia, USA, August 2006 (inproceedings)

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Programmable central pattern generators: an application to biped locomotion control

Righetti, L., Ijspeert, A.

In Proceedings of the IEEE International Conference on Robotics and Automation, 2006. ICRA 2006., pages: 1585-1590, IEEE, 2006 (inproceedings)

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[BibTex]

[BibTex]