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2016


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Wireless actuation with functional acoustic surfaces

Qiu, T., Palagi, S., Mark, A. G., Melde, K., Adams, F., Fischer, P.

Appl. Phys. Lett., 109(19):191602, November 2016, APL Editor's pick. APL News. (article)

Abstract
Miniaturization calls for micro-actuators that can be powered wirelessly and addressed individually. Here, we develop functional surfaces consisting of arrays of acoustically resonant microcavities, and we demonstrate their application as two-dimensional wireless actuators. When remotely powered by an acoustic field, the surfaces provide highly directional propulsive forces in fluids through acoustic streaming. A maximal force of similar to 0.45mN is measured on a 4 x 4 mm(2) functional surface. The response of the surfaces with bubbles of different sizes is characterized experimentally. This shows a marked peak around the micro-bubbles' resonance frequency, as estimated by both an analytical model and numerical simulations. The strong frequency dependence can be exploited to address different surfaces with different acoustic frequencies, thus achieving wireless actuation with multiple degrees of freedom. The use of the functional surfaces as wireless ready-to-attach actuators is demonstrated by implementing a wireless and bidirectional miniaturized rotary motor, which is 2.6 x 2.6 x 5 mm(3) in size and generates a stall torque of similar to 0.5 mN.mm. The adoption of micro-structured surfaces as wireless actuators opens new possibilities in the development of miniaturized devices and tools for fluidic environments that are accessible by low intensity ultrasound fields.

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link (url) DOI Project Page [BibTex]

2016


link (url) DOI Project Page [BibTex]


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Nanomotors

Alarcon-Correa, M., Walker (Schamel), D., Qiu, T., Fischer, P.

Eur. Phys. J.-Special Topics, 225(11-12):2241-2254, November 2016 (article)

Abstract
This minireview discusses whether catalytically active macromolecules and abiotic nanocolloids, that are smaller than motile bacteria, can self-propel. Kinematic reversibility at low Reynolds number demands that self-propelling colloids must break symmetry. Methods that permit the synthesis and fabrication of Janus nanocolloids are therefore briefly surveyed, as well as means that permit the analysis of the nanocolloids' motion. Finally, recent work is reviewed which shows that nanoagents are small enough to penetrate the complex inhomogeneous polymeric network of biological fluids and gels, which exhibit diverse rheological behaviors.

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DOI [BibTex]

DOI [BibTex]


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Structured light enables biomimetic swimming and versatile locomotion of photoresponsive soft microrobots

Palagi, S., Mark, A. G., Reigh, S. Y., Melde, K., Qiu, T., Zeng, H., Parmeggiani, C., Martella, D., Sanchez-Castillo, A., Kapernaum, N., Giesselmann, F., Wiersma, D. S., Lauga, E., Fischer, P.

Nature Materials, 15(6):647–653, November 2016, Max Planck press release, Nature News & Views. (article)

Abstract
Microorganisms move in challenging environments by periodic changes in body shape. In contrast, current artificial microrobots cannot actively deform, exhibiting at best passive bending under external fields. Here, by taking advantage of the wireless, scalable and spatiotemporally selective capabilities that light allows, we show that soft microrobots consisting of photoactive liquid-crystal elastomers can be driven by structured monochromatic light to perform sophisticated biomimetic motions. We realize continuum yet selectively addressable artificial microswimmers that generate travelling-wave motions to self-propel without external forces or torques, as well as microrobots capable of versatile locomotion behaviours on demand. Both theoretical predictions and experimental results confirm that multiple gaits, mimicking either symplectic or antiplectic metachrony of ciliate protozoa, can be achieved with single microswimmers. The principle of using structured light can be extended to other applications that require microscale actuation with sophisticated spatiotemporal coordination for advanced microrobotic technologies.

pf

Video - Soft photo Micro-Swimmer DOI [BibTex]

Video - Soft photo Micro-Swimmer DOI [BibTex]


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An electro-active polymer based lens module for dynamically varying focal system

Yun, S., Park, S., Nam, S., Park, B., Park, S. K., Mun, S., Lim, J. M., Kyung, K.

Applied Physics Letters, 109(14):141908, October 2016 (article)

Abstract
We demonstrate a polymer-based active-lens module allowing a dynamic focus controllable optical system with a wide tunable range. The active-lens module is composed of parallelized two active- lenses with a convex and a concave shaped hemispherical lens structure, respectively. Under opera- tion with dynamic input voltage signals, each active-lens produces translational movement bi-directionally responding to a hybrid driving force that is a combination of an electro-active response of a thin dielectric elastomer membrane and an electro-static attraction force. Since the proposed active lens module widely modulates a gap-distance between lens-elements, an optical system based on the active-lens module provides widely-variable focusing for selective imaging of objects in arbitrary position.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Wrinkle structures formed by formulating UV-crosslinkable liquid prepolymers

Park, S. K., Kwark, Y., Nam, S., Park, S., Park, B., Yun, S., Moon, J., Lee, J., Yu, B., Kyung, K.

Polymer, 99, pages: 447-452, September 2016 (article)

Abstract
Artificial wrinkles have recently been in the spotlight due to their potential use in high-tech applications. A spontaneously wrinkled film can be fabricated from UV-crosslinkable liquid prepolymers. Here, we controlled the wrinkle formation by simply formulating two UV-crosslinkable liquid prepolymers, tetraethylene glycol bis(4-ethenyl-2,3,5,6-tetrafluorophenyl) ether (TEGDSt) and tetraethylene glycol diacrylate (TEGDA). The wrinkles were formed from the TEGDSt/TEGDA formulated prepolymer layers containing up to 30 wt% of TEGDA. The wrinkle formation depended upon the rate of photo-crosslinking reaction of the formulated prepolymers. The first order apparent rate constant, kapp, was between ca. 5.7 × 10−3 and 12.2 × 10−3 s−1 for the wrinkle formation. The wrinkle structures were modulated within the kapp mainly due to variation in the extent of shrinkage of the formulated prepolymer layers with the content of TEGDA

hi

link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Capture of 2D Microparticle Arrays via a UV-Triggered Thiol-yne “Click” Reaction

Walker (Schamel), D., Singh, D. P., Fischer, P.

Advanced Materials, 28(44):9846-9850, September 2016 (article)

Abstract
Immobilization of colloidal assemblies onto solid supports via a fast UV-triggered click-reaction is achieved. Transient assemblies of microparticles and colloidal materials can be captured and transferred to solid supports. The technique does not require complex reaction conditions, and is compatible with a variety of particle assembly methods.

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DOI [BibTex]


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Magnesium plasmonics for UV applications and chiral sensing

Jeong, H. H., Mark, A. G., Fischer, P.

Chem. Comm., 52(82):12179-12182, September 2016 (article)

Abstract
We demonstrate that chiral magnesium nanoparticles show remarkable plasmonic extinction- and chiroptical-effects in the ultraviolet region. The Mg nanohelices possess an enhanced local surface plasmon resonance (LSPR) sensitivity due to the strong dispersion of most substances in the UV region.

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DOI [BibTex]

DOI [BibTex]


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Holograms for acoustics

Melde, K., Mark, A. G., Qiu, T., Fischer, P.

Nature, 537, pages: 518-522, September 2016, Max Planck press release, Nature News & Views, Nature Video. (article)

Abstract
Holographic techniques are fundamental to applications such as volumetric displays(1), high-density data storage and optical tweezers that require spatial control of intricate optical(2) or acoustic fields(3,4) within a three-dimensional volume. The basis of holography is spatial storage of the phase and/or amplitude profile of the desired wavefront(5,6) in a manner that allows that wavefront to be reconstructed by interference when the hologram is illuminated with a suitable coherent source. Modern computer-generated holography(7) skips the process of recording a hologram from a physical scene, and instead calculates the required phase profile before rendering it for reconstruction. In ultrasound applications, the phase profile is typically generated by discrete and independently driven ultrasound sources(3,4,8-12); however, these can only be used in small numbers, which limits the complexity or degrees of freedom that can be attained in the wavefront. Here we introduce monolithic acoustic holograms, which can reconstruct diffraction-limited acoustic pressure fields and thus arbitrary ultrasound beams. We use rapid fabrication to craft the holograms and achieve reconstruction degrees of freedom two orders of magnitude higher than commercial phased array sources. The technique is inexpensive, appropriate for both transmission and reflection elements, and scales well to higher information content, larger aperture size and higher power. The complex three-dimensional pressure and phase distributions produced by these acoustic holograms allow us to demonstrate new approaches to controlled ultrasonic manipulation of solids in water, and of liquids and solids in air. We expect that acoustic holograms will enable new capabilities in beam-steering and the contactless transfer of power, improve medical imaging, and drive new applications of ultrasound.

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Video - Holograms for Sound DOI Project Page [BibTex]

Video - Holograms for Sound DOI Project Page [BibTex]


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A loop-gap resonator for chirality-sensitive nuclear magneto-electric resonance (NMER)

Garbacz, P., Fischer, P., Kraemer, S.

J. Chem. Phys., 145(10):104201, September 2016 (article)

Abstract
Direct detection of molecular chirality is practically impossible by methods of standard nuclear magnetic resonance (NMR) that is based on interactions involving magnetic-dipole and magnetic-field operators. However, theoretical studies provide a possible direct probe of chirality by exploiting an enantiomer selective additional coupling involving magnetic-dipole, magnetic-field, and electric field operators. This offers a way for direct experimental detection of chirality by nuclear magneto-electric resonance (NMER). This method uses both resonant magnetic and electric radiofrequency (RF) fields. The weakness of the chiral interaction though requires a large electric RF field and a small transverse RF magnetic field over the sample volume, which is a non-trivial constraint. In this study, we present a detailed study of the NMER concept and a possible experimental realization based on a loop-gap resonator. For this original device, the basic principle and numerical studies as well as fabrication and measurements of the frequency dependence of the scattering parameter are reported. By simulating the NMER spin dynamics for our device and taking the F-19 NMER signal of enantiomer-pure 1,1,1-trifluoropropan-2-ol, we predict a chirality induced NMER signal that accounts for 1%-5% of the standard achiral NMR signal. Published by AIP Publishing.

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DOI [BibTex]

DOI [BibTex]


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Active Nanorheology with Plasmonics

Jeong, H. H., Mark, A. G., Lee, T., Alarcon-Correa, M., Eslami, S., Qiu, T., Gibbs, J. G., Fischer, P.

Nano Letters, 16(8):4887-4894, July 2016 (article)

Abstract
Nanoplasmonic systems are valued for their strong optical response and their small size. Most plasmonic sensors and systems to date have been rigid and passive. However, rendering these structures dynamic opens new possibilities for applications. Here we demonstrate that dynamic plasmonic nanoparticles can be used as mechanical sensors to selectively probe the rheological properties of a fluid in situ at the nanoscale and in microscopic volumes. We fabricate chiral magneto-plasmonic nanocolloids that can be actuated by an external magnetic field, which in turn allows for the direct and fast modulation of their distinct optical response. The method is robust and allows nanorheological measurements with a mechanical sensitivity of similar to 0.1 cP, even in strongly absorbing fluids with an optical density of up to OD similar to 3 (similar to 0.1% light transmittance) and in the presence of scatterers (e.g., 50% v/v red blood cells).

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DOI [BibTex]

DOI [BibTex]


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Objective assessment of robotic surgical skill using instrument contact vibrations

Gomez, E. D., Aggarwal, R., McMahan, W., Bark, K., Kuchenbecker, K. J.

Surgical Endoscopy, 30(4):1419-1431, 2016 (article)

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[BibTex]

[BibTex]


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Dispersion and shape engineered plasmonic nanosensors

Jeong, H. H., Mark, A. G., Alarcon-Correa, M., Kim, I., Oswald, P., Lee, T. C., Fischer, P.

Nature Communications, 7, pages: 11331, March 2016 (article)

Abstract
Biosensors based on the localized surface plasmon resonance (LSPR) of individual metallic nanoparticles promise to deliver modular, low-cost sensing with high-detection thresholds. However, they continue to suffer from relatively low sensitivity and figures of merit (FOMs). Herein we introduce the idea of sensitivity enhancement of LSPR sensors through engineering of the material dispersion function. Employing dispersion and shape engineering of chiral nanoparticles leads to remarkable refractive index sensitivities (1,091 nmRIU(-1) at lambda = 921 nm) and FOMs (>2,800 RIU-1). A key feature is that the polarization-dependent extinction of the nanoparticles is now characterized by rich spectral features, including bipolar peaks and nulls, suitable for tracking refractive index changes. This sensing modality offers strong optical contrast even in the presence of highly absorbing media, an important consideration for use in complex biological media with limited transmission. The technique is sensitive to surface-specific binding events which we demonstrate through biotin-avidin surface coupling.

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link (url) DOI [BibTex]


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Cutaneous Feedback of Fingertip Deformation and Vibration for Palpation in Robotic Surgery

Pacchierotti, C., Prattichizzo, D., Kuchenbecker, K. J.

IEEE Transactions on Biomedical Engineering, 63(2):278-287, February 2016 (article)

hi

[BibTex]

[BibTex]


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Structure modulated electrostatic deformable mirror for focus and geometry control

Nam, S., Park, S., Yun, S., Park, B., Park, S. K., Kyung, K.

Optics Express, 24(1):55-66, OSA, January 2016 (article)

Abstract
We suggest a way to electrostatically control deformed geometry of an electrostatic deformable mirror (EDM) based on geometric modulation of a basement. The EDM is composed of a metal coated elastomeric membrane (active mirror) and a polymeric basement with electrode (ground). When an electrical voltage is applied across the components, the active mirror deforms toward the stationary basement responding to electrostatic attraction force in an air gap. Since the differentiated gap distance can induce change in electrostatic force distribution between the active mirror and the basement, the EDMs are capable of controlling deformed geometry of the active mirror with different basement structures (concave, flat, and protrusive). The modulation of the deformed geometry leads to significant change in the range of the focal length of the EDMs. Even under dynamic operations, the EDM shows fairly consistent and large deformation enough to change focal length in a wide frequency range (1~175 Hz). The geometric modulation of the active mirror with dynamic focus tunability can allow the EDM to be an active mirror lens for optical zoom devices as well as an optical component controlling field of view.

hi

link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Magnetic Propulsion of Microswimmers with DNA-Based Flagellar Bundles

Maier, A. M., Weig, C., Oswald, P., Frey, E., Fischer, P., Liedl, T.

Nano Letters, 16(2):906-910, January 2016 (article)

Abstract
We show that DNA-based self-assembly can serve as a general and flexible tool to construct artificial flagella of several micrometers in length and only tens of nanometers in diameter. By attaching the DNA flagella to biocompatible magnetic microparticles, we provide a proof of concept demonstration of hybrid structures that, when rotated in an external magnetic field, propel by means of a flagellar bundle, similar to self-propelling peritrichous bacteria. Our theoretical analysis predicts that flagellar bundles that possess a length-dependent bending stiffness should exhibit a superior swimming speed compared to swimmers with a single appendage. The DNA self-assembly method permits the realization of these improved flagellar bundles in good agreement with our quantitative model. DNA flagella with well-controlled shape could fundamentally increase the functionality of fully biocompatible nanorobots and extend the scope and complexity of active materials.

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DOI [BibTex]

DOI [BibTex]


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Peripheral vs. central determinants of vibrotactile adaptation

Klöcker, A., Gueorguiev, D., Thonnard, J. L., Mouraux, A.

Journal of Neurophysiology, 115(2):685-691, 2016, PMID: 26581868 (article)

Abstract
Long-lasting mechanical vibrations applied to the skin induce a reversible decrease in the perception of vibration at the stimulated skin site. This phenomenon of vibrotactile adaptation has been studied extensively, yet there is still no clear consensus on the mechanisms leading to vibrotactile adaptation. In particular, the respective contributions of 1) changes affecting mechanical skin impedance, 2) peripheral processes, and 3) central processes are largely unknown. Here we used direct electrical stimulation of nerve fibers to bypass mechanical transduction processes and thereby explore the possible contribution of central vs. peripheral processes to vibrotactile adaptation. Three experiments were conducted. In the first, adaptation was induced with mechanical vibration of the fingertip (51- or 251-Hz vibration delivered for 8 min, at 40× detection threshold). In the second, we attempted to induce adaptation with transcutaneous electrical stimulation of the median nerve (51- or 251-Hz constant-current pulses delivered for 8 min, at 1.5× detection threshold). Vibrotactile detection thresholds were measured before and after adaptation. Mechanical stimulation induced a clear increase of vibrotactile detection thresholds. In contrast, thresholds were unaffected by electrical stimulation. In the third experiment, we assessed the effect of mechanical adaptation on the detection thresholds to transcutaneous electrical nerve stimuli, measured before and after adaptation. Electrical detection thresholds were unaffected by the mechanical adaptation. Taken together, our results suggest that vibrotactile adaptation is predominantly the consequence of peripheral mechanoreceptor processes and/or changes in biomechanical properties of the skin.

hi

link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Silent Expectations: Dynamic Causal Modeling of Cortical Prediction and Attention to Sounds That Weren’t

Chennu, S., Noreika, V., Gueorguiev, D., Shtyrov, Y., Bekinschtein, T. A., Henson, R.

Journal of Neuroscience, 36(32):8305-8316, Society for Neuroscience, 2016 (article)

Abstract
There is increasing evidence that human perception is realized by a hierarchy of neural processes in which predictions sent backward from higher levels result in prediction errors that are fed forward from lower levels, to update the current model of the environment. Moreover, the precision of prediction errors is thought to be modulated by attention. Much of this evidence comes from paradigms in which a stimulus differs from that predicted by the recent history of other stimuli (generating a so-called {\textquotedblleft}mismatch response{\textquotedblright}). There is less evidence from situations where a prediction is not fulfilled by any sensory input (an {\textquotedblleft}omission{\textquotedblright} response). This situation arguably provides a more direct measure of {\textquotedblleft}top-down{\textquotedblright} predictions in the absence of confounding {\textquotedblleft}bottom-up{\textquotedblright} input. We applied Dynamic Causal Modeling of evoked electromagnetic responses recorded by EEG and MEG to an auditory paradigm in which we factorially crossed the presence versus absence of {\textquotedblleft}bottom-up{\textquotedblright} stimuli with the presence versus absence of {\textquotedblleft}top-down{\textquotedblright} attention. Model comparison revealed that both mismatch and omission responses were mediated by increased forward and backward connections, differing primarily in the driving input. In both responses, modeling results suggested that the presence of attention selectively modulated backward {\textquotedblleft}prediction{\textquotedblright} connections. Our results provide new model-driven evidence of the pure top-down prediction signal posited in theories of hierarchical perception, and highlight the role of attentional precision in strengthening this prediction.SIGNIFICANCE STATEMENT Human auditory perception is thought to be realized by a network of neurons that maintain a model of and predict future stimuli. Much of the evidence for this comes from experiments where a stimulus unexpectedly differs from previous ones, which generates a well-known {\textquotedblleft}mismatch response.{\textquotedblright} But what happens when a stimulus is unexpectedly omitted altogether? By measuring the brain{\textquoteright}s electromagnetic activity, we show that it also generates an {\textquotedblleft}omission response{\textquotedblright} that is contingent on the presence of attention. We model these responses computationally, revealing that mismatch and omission responses only differ in the location of inputs into the same underlying neuronal network. In both cases, we show that attention selectively strengthens the brain{\textquoteright}s prediction of the future.

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link (url) DOI [BibTex]

link (url) DOI [BibTex]


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Touch uses frictional cues to discriminate flat materials

Gueorguiev, D., Bochereau, S., Mouraux, A., Hayward, V., Thonnard, J.

Scientific reports, 6, pages: 25553, Nature Publishing Group, 2016 (article)

hi

[BibTex]

[BibTex]

2010


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Lack of Discriminatory Function for Endoscopy Skills on a Computer-based Simulator

Kim, S., Spencer, G., Makar, G., Ahmad, N., Jaffe, D., Ginsberg, G., Kuchenbecker, K. J., Kochman, M.

Surgical Endoscopy, 24(12):3008-3015, December 2010 (article)

hi

[BibTex]

2010


[BibTex]


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Identifying the Role of Proprioception in Upper-Limb Prosthesis Control: Studies on Targeted Motion

Blank, A., Okamura, A. M., Kuchenbecker, K. J.

ACM Transactions on Applied Perception, 7(3):1-23, June 2010 (article)

hi

[BibTex]

[BibTex]


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Molecular QED of coherent and incoherent sum-frequency and second-harmonic generation in chiral liquids in the presence of a static electric field

Fischer, P., Salam, A.

MOLECULAR PHYSICS, 108(14):1857-1868, 2010 (article)

Abstract
Coherent second-order nonlinear optical processes are symmetry forbidden in centrosymmetric environments in the electric-dipole approximation. In liquids that contain chiral molecules, however, and which therefore lack mirror image symmetry, coherent sum-frequency generation is possible, whereas second-harmonic generation remains forbidden. Here we apply the theory of molecular quantum electrodynamics to the calculation of the matrix element, transition rate, and integrated signal intensity for sum-frequency and second-harmonic generation taking place in a chiral liquid in the presence and absence of a static electric field, to examine which coherent and incoherent processes exist in the electric-dipole approximation in liquids. Third- and fourth-order time-dependent perturbation theory is employed in combination with single-sided Feynman diagrams to evaluate two contributions arising from static field-free and field-induced processes. It is found that, in addition to the coherent term, an incoherent process exists for sum-frequency generation in liquids. Surprisingly, in the case of dc-field-induced second-harmonic generation, the incoherent contribution is found to always vanish for isotropic chiral liquids even though hyper-Rayleigh second-harmonic generation and electric-field-induced second-harmonic generation are both independently symmetry allowed in any liquid.

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DOI [BibTex]


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Goal-Oriented Control of Self-Organizing Behavior in Autonomous Robots

Martius, G.

Georg-August-Universität Göttingen, 2010 (phdthesis)

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link (url) [BibTex]

2005


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Contact Location Display for Haptic Perception of Curvature and Object Motion

Provancher, W. R., Cutkosky, M. R., Kuchenbecker, K. J., Niemeyer, G.

International Journal of Robotics Research, 24(9):691-702, sep 2005 (article)

hi

[BibTex]

2005


[BibTex]


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Nonlinear optical spectroscopy of chiral molecules

Fischer, P., Hache, F.

CHIRALITY, 17(8):421-437, 2005 (article)

Abstract
We review nonlinear optical processes that are specific to chiral molecules in solution and on surfaces. In contrast to conventional natural optical activity phenomena, which depend linearly on the electric field strength of the optical field, we discuss how optical processes that are nonlinear (quadratic, cubic, and quartic) functions of the electromagnetic field strength may probe optically active centers and chiral vibrations. We show that nonlinear techniques open entirely new ways of exploring chirality in chemical and biological systems: The cubic processes give rise to nonlinear circular dichroism and nonlinear optical rotation and make it possible to observe dynamic chiral processes at ultrafast time scales. The quadratic second-harmonic and sum-frequency-generation phenomena and the quartic processes may arise entirely in the electric-dipole approximation and do not require the use of circularly polarized light to detect chirality: They provide surface selectivity and their observables can be relatively much larger than in linear optical activity. These processes also give rise to the generation of light at a new color, and in liquids this frequency conversion only occurs if the solution is optically active. We survey recent chiral nonlinear optical experiments and give examples of their application to problems of biophysical interest. (C) 2005 Wiley-Liss, Inc.

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DOI [BibTex]

DOI [BibTex]


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Negative refraction at optical frequencies in nonmagnetic two-component molecular media

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

PHYSICAL REVIEW LETTERS, 95(6), 2005 (article)

Abstract
There is significant motivation to develop media with negative refractive indices at optical frequencies, but efforts in this direction are hampered by the weakness of the magnetic response at such frequencies. We show theoretically that a nonmagnetic medium with two atomic or molecular constituents can exhibit a negative refractive index. A negative index is possible even when the real parts of both the permittivity and permeability are positive. This surprising result provides a route to isotropic negative-index media at optical frequencies.

pf

DOI [BibTex]

DOI [BibTex]

2003


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New electro-optic effect: Sum-frequency generation from optically active liquids in the presence of a dc electric field

Fischer, P., Buckingham, A., Beckwitt, K., Wiersma, D., Wise, F.

PHYSICAL REVIEW LETTERS, 91(17), 2003 (article)

Abstract
We report the observation of sum-frequency signals that depend linearly on an applied electrostatic field and that change sign with the handedness of an optically active solute. This recently predicted chiral electro-optic effect exists in the electric-dipole approximation. The static electric field gives rise to an electric-field-induced sum-frequency signal (an achiral third-order process) that interferes with the chirality-specific sum-frequency at second order. The cross-terms linear in the electrostatic field constitute the effect and may be used to determine the absolute sign of second- and third-order nonlinear-optical susceptibilities in isotropic media.

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DOI [BibTex]

2003


DOI [BibTex]


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Chiral and achiral contributions to sum-frequency generation from optically active solutions of binaphthol

Fischer, P., Wise, F., Albrecht, A.

JOURNAL OF PHYSICAL CHEMISTRY A, 107(40):8232-8238, 2003 (article)

Abstract
The nonlinear sum- and difference-frequency generation spectroscopies can be probes of molecular chirality in optically active systems. We present a tensorial analysis of the chirality-specific electric-dipolar sum-frequency-generation susceptibility and the achiral electric-quadrupolar and magnetic-dipolar nonlinearities at second order in isotropic media. The chiral and achiral contributions to the sum-frequency signal from the bulk of optically active solutions of 1,1'-bi-2-naphthol (2,2'-dehydroxy-1,1'-binaphthyl) can be distinguished, and the former dominates. Ab initio computations reveal the dramatic resonance enhancement that the isotropic component of the electric-dipolar three-wave mixing hyperpolarizability experiences. Away from resonance its magnitude rapidly decreases, as-unlike the vector component-it is zero in the static limit. The dispersion of the first hyperpolarizability is computed by a configuration interaction singles sum-over-states approach with explicit regard to the Franck-Condon active vibrational substructure for all resonant electronic states.

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DOI [BibTex]

DOI [BibTex]