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2013


Branch\&Rank for Efficient Object Detection
Branch&Rank for Efficient Object Detection

Lehmann, A., Gehler, P., VanGool, L.

International Journal of Computer Vision, Springer, December 2013 (article)

Abstract
Ranking hypothesis sets is a powerful concept for efficient object detection. In this work, we propose a branch&rank scheme that detects objects with often less than 100 ranking operations. This efficiency enables the use of strong and also costly classifiers like non-linear SVMs with RBF-TeX kernels. We thereby relieve an inherent limitation of branch&bound methods as bounds are often not tight enough to be effective in practice. Our approach features three key components: a ranking function that operates on sets of hypotheses and a grouping of these into different tasks. Detection efficiency results from adaptively sub-dividing the object search space into decreasingly smaller sets. This is inherited from branch&bound, while the ranking function supersedes a tight bound which is often unavailable (except for rather limited function classes). The grouping makes the system effective: it separates image classification from object recognition, yet combines them in a single formulation, phrased as a structured SVM problem. A novel aspect of branch&rank is that a better ranking function is expected to decrease the number of classifier calls during detection. We use the VOC’07 dataset to demonstrate the algorithmic properties of branch&rank.

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pdf link (url) [BibTex]

2013


pdf link (url) [BibTex]


Extracting Postural Synergies for Robotic Grasping
Extracting Postural Synergies for Robotic Grasping

Romero, J., Feix, T., Ek, C., Kjellstrom, H., Kragic, D.

Robotics, IEEE Transactions on, 29(6):1342-1352, December 2013 (article)

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[BibTex]

[BibTex]


Markov Random Field Modeling, Inference & Learning in Computer Vision & Image Understanding: A Survey
Markov Random Field Modeling, Inference & Learning in Computer Vision & Image Understanding: A Survey

Wang, C., Komodakis, N., Paragios, N.

Computer Vision and Image Understanding (CVIU), 117(11):1610-1627, November 2013 (article)

Abstract
In this paper, we present a comprehensive survey of Markov Random Fields (MRFs) in computer vision and image understanding, with respect to the modeling, the inference and the learning. While MRFs were introduced into the computer vision field about two decades ago, they started to become a ubiquitous tool for solving visual perception problems around the turn of the millennium following the emergence of efficient inference methods. During the past decade, a variety of MRF models as well as inference and learning methods have been developed for addressing numerous low, mid and high-level vision problems. While most of the literature concerns pairwise MRFs, in recent years we have also witnessed significant progress in higher-order MRFs, which substantially enhances the expressiveness of graph-based models and expands the domain of solvable problems. This survey provides a compact and informative summary of the major literature in this research topic.

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Publishers site pdf [BibTex]

Publishers site pdf [BibTex]


Vision meets Robotics: The {KITTI} Dataset
Vision meets Robotics: The KITTI Dataset

Geiger, A., Lenz, P., Stiller, C., Urtasun, R.

International Journal of Robotics Research, 32(11):1231 - 1237 , Sage Publishing, September 2013 (article)

Abstract
We present a novel dataset captured from a VW station wagon for use in mobile robotics and autonomous driving research. In total, we recorded 6 hours of traffic scenarios at 10-100 Hz using a variety of sensor modalities such as high-resolution color and grayscale stereo cameras, a Velodyne 3D laser scanner and a high-precision GPS/IMU inertial navigation system. The scenarios are diverse, capturing real-world traffic situations and range from freeways over rural areas to inner-city scenes with many static and dynamic objects. Our data is calibrated, synchronized and timestamped, and we provide the rectified and raw image sequences. Our dataset also contains object labels in the form of 3D tracklets and we provide online benchmarks for stereo, optical flow, object detection and other tasks. This paper describes our recording platform, the data format and the utilities that we provide.

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pdf DOI [BibTex]

pdf DOI [BibTex]


Unscented Kalman Filtering on Riemannian Manifolds
Unscented Kalman Filtering on Riemannian Manifolds

Soren Hauberg, Francois Lauze, Kim S. Pedersen

Journal of Mathematical Imaging and Vision, 46(1):103-120, Springer Netherlands, May 2013 (article)

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Publishers site PDF [BibTex]

Publishers site PDF [BibTex]


Quasi-Newton Methods: A New Direction
Quasi-Newton Methods: A New Direction

Hennig, P., Kiefel, M.

Journal of Machine Learning Research, 14(1):843-865, March 2013 (article)

Abstract
Four decades after their invention, quasi-Newton methods are still state of the art in unconstrained numerical optimization. Although not usually interpreted thus, these are learning algorithms that fit a local quadratic approximation to the objective function. We show that many, including the most popular, quasi-Newton methods can be interpreted as approximations of Bayesian linear regression under varying prior assumptions. This new notion elucidates some shortcomings of classical algorithms, and lights the way to a novel nonparametric quasi-Newton method, which is able to make more efficient use of available information at computational cost similar to its predecessors.

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website+code pdf link (url) [BibTex]

website+code pdf link (url) [BibTex]


Hybrid nanocolloids with programmed three-dimensional shape and material composition
Hybrid nanocolloids with programmed three-dimensional shape and material composition

Mark, A. G., Gibbs, J. G., Lee, T., Fischer, P.

NATURE MATERIALS, 12(9):802-807, 2013, Max Planck Press Release. (article)

Abstract
Tuning the optical(1,2), electromagnetic(3,4) and mechanical properties of a material requires simultaneous control over its composition and shape(5). This is particularly challenging for complex structures at the nanoscale because surface-energy minimization generally causes small structures to be highly symmetric(5). Here we combine low-temperature shadow deposition with nanoscale patterning to realize nanocolloids with anisotropic three-dimensional shapes, feature sizes down to 20 nm and a wide choice of materials. We demonstrate the versatility of the fabrication scheme by growing three-dimensional hybrid nanostructures that contain several functional materials with the lowest possible symmetry, and by fabricating hundreds of billions of plasmonic nanohelices, which we use as chiral metafluids with record circular dichroism and tunable chiroptical properties.

Max Planck Press Release.

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Video - Fabrication of Designer Nanostructures DOI [BibTex]


Chiral Colloidal Molecules And Observation of The Propeller Effect
Chiral Colloidal Molecules And Observation of The Propeller Effect

Schamel, D., Pfeifer, M., Gibbs, J. G., Miksch, B., Mark, A. G., Fischer, P.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 135(33):12353-12359, 2013 (article)

Abstract
Chiral molecules play an important role in biological and chemical processes, but physical effects due to their symmetry-breaking are generally weak. Several physical chiral separation schemes which could potentially be useful, including the propeller effect, have therefore not yet been demonstrated at the molecular scale. However, it has been proposed that complex nonspherical colloidal particles could act as ``colloidal molecules{''} in mesoscopic model systems to permit the visualization of molecular phenomena that are otherwise difficult to observe. Unfortunately, it is difficult to synthesize such colloids because surface minimization generally favors the growth of symmetric particles. Here we demonstrate the production of large numbers of complex colloids with glancing angle physical vapor deposition. We use chiral colloids to demonstrate the Baranova and Zel'dovich (Baranova, N. B.; Zel'dovich, B. Y. Chem. Phys. Lett. 1978, 57, 435) propeller effect: the separation of a racemic mixture by application of a rotating field that couples to the dipole moment of the enantiomers and screw propels them in opposite directions. The handedness of the colloidal suspensions is monitored with circular differential light scattering. An exact solution for the colloid's propulsion is derived, and comparisons between the colloidal system and the corresponding effect at the molecular scale are made.

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Video - Nanospropellers DOI [BibTex]

Video - Nanospropellers DOI [BibTex]


Indirect absorption spectroscopy using quantum cascade lasers: mid-infrared refractometry and photothermal spectroscopy
Indirect absorption spectroscopy using quantum cascade lasers: mid-infrared refractometry and photothermal spectroscopy

Pfeifer, M., Ruf, A., Fischer, P.

OPTICS EXPRESS, 21(22):25643-25654, 2013 (article)

Abstract
We record vibrational spectra with two indirect schemes that depend on the real part of the index of refraction: mid-infrared refractometry and photothermal spectroscopy. In the former, a quantum cascade laser (QCL) spot is imaged to determine the angles of total internal reflection, which yields the absorption line via a beam profile analysis. In the photothermal measurements, a tunable QCL excites vibrational resonances of a molecular monolayer, which heats the surrounding medium and changes its refractive index. This is observed with a probe laser in the visible. Sub-monolayer sensitivities are demonstrated. (C) 2013 Optical Society of America

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DOI [BibTex]


Plasmonic nanohelix metamaterials with tailorable giant circular dichroism
Plasmonic nanohelix metamaterials with tailorable giant circular dichroism

Gibbs, J. G., Mark, A. G., Eslami, S., Fischer, P.

APPLIED PHYSICS LETTERS, 103(21), 2013, Featured cover article. (article)

Abstract
Plasmonic nanohelix arrays are shown to interact with electromagnetic fields in ways not typically seen with ordinary matter. Chiral metamaterials (CMMs) with feature sizes small with respect to the wavelength of visible light are a promising route to experimentally achieve such phenomena as negative refraction without the need for simultaneously negative e and mu. Here we not only show that giant circular dichroism in the visible is achievable with hexagonally arranged plasmonic nanohelix arrays, but that we can precisely tune the optical activity via morphology and lattice spacing. The discrete dipole approximation is implemented to support experimental data. (C) 2013 AIP Publishing LLC.

Featured cover article.

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DOI [BibTex]

DOI [BibTex]


Random Forests for Real Time {3D} Face Analysis
Random Forests for Real Time 3D Face Analysis

Fanelli, G., Dantone, M., Gall, J., Fossati, A., van Gool, L.

International Journal of Computer Vision, 101(3):437-458, Springer, 2013 (article)

Abstract
We present a random forest-based framework for real time head pose estimation from depth images and extend it to localize a set of facial features in 3D. Our algorithm takes a voting approach, where each patch extracted from the depth image can directly cast a vote for the head pose or each of the facial features. Our system proves capable of handling large rotations, partial occlusions, and the noisy depth data acquired using commercial sensors. Moreover, the algorithm works on each frame independently and achieves real time performance without resorting to parallel computations on a GPU. We present extensive experiments on publicly available, challenging datasets and present a new annotated head pose database recorded using a Microsoft Kinect.

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data and code publisher's site pdf DOI Project Page [BibTex]

data and code publisher's site pdf DOI Project Page [BibTex]


Markerless Motion Capture of Multiple Characters Using Multi-view Image Segmentation
Markerless Motion Capture of Multiple Characters Using Multi-view Image Segmentation

Liu, Y., Gall, J., Stoll, C., Dai, Q., Seidel, H., Theobalt, C.

Transactions on Pattern Analysis and Machine Intelligence, 35(11):2720-2735, 2013 (article)

Abstract
Capturing the skeleton motion and detailed time-varying surface geometry of multiple, closely interacting peoples is a very challenging task, even in a multicamera setup, due to frequent occlusions and ambiguities in feature-to-person assignments. To address this task, we propose a framework that exploits multiview image segmentation. To this end, a probabilistic shape and appearance model is employed to segment the input images and to assign each pixel uniquely to one person. Given the articulated template models of each person and the labeled pixels, a combined optimization scheme, which splits the skeleton pose optimization problem into a local one and a lower dimensional global one, is applied one by one to each individual, followed with surface estimation to capture detailed nonrigid deformations. We show on various sequences that our approach can capture the 3D motion of humans accurately even if they move rapidly, if they wear wide apparel, and if they are engaged in challenging multiperson motions, including dancing, wrestling, and hugging.

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data and video pdf DOI Project Page [BibTex]

data and video pdf DOI Project Page [BibTex]


Viewpoint and pose in body-form adaptation
Viewpoint and pose in body-form adaptation

Sekunova, A., Black, M., Parkinson, L., Barton, J. J. S.

Perception, 42(2):176-186, 2013 (article)

Abstract
Faces and bodies are complex structures, perception of which can play important roles in person identification and inference of emotional state. Face representations have been explored using behavioural adaptation: in particular, studies have shown that face aftereffects show relatively broad tuning for viewpoint, consistent with origin in a high-level structural descriptor far removed from the retinal image. Our goals were to determine first, if body aftereffects also showed a degree of viewpoint invariance, and second if they also showed pose invariance, given that changes in pose create even more dramatic changes in the 2-D retinal image. We used a 3-D model of the human body to generate headless body images, whose parameters could be varied to generate different body forms, viewpoints, and poses. In the first experiment, subjects adapted to varying viewpoints of either slim or heavy bodies in a neutral stance, followed by test stimuli that were all front-facing. In the second experiment, we used the same front-facing bodies in neutral stance as test stimuli, but compared adaptation from bodies in the same neutral stance to adaptation with the same bodies in different poses. We found that body aftereffects were obtained over substantial viewpoint changes, with no significant decline in aftereffect magnitude with increasing viewpoint difference between adapting and test images. Aftereffects also showed transfer across one change in pose but not across another. We conclude that body representations may have more viewpoint invariance than faces, and demonstrate at least some transfer across pose, consistent with a high-level structural description. Keywords: aftereffect, shape, face, representation

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pdf from publisher abstract pdf link (url) Project Page [BibTex]

pdf from publisher abstract pdf link (url) Project Page [BibTex]


Class-Specific Hough Forests for Object Detection
Class-Specific Hough Forests for Object Detection

Gall, J., Lempitsky, V.

In Decision Forests for Computer Vision and Medical Image Analysis, pages: 143-157, 11, (Editors: Criminisi, A. and Shotton, J.), Springer, 2013 (incollection)

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code Project Page [BibTex]

code Project Page [BibTex]


Non-parametric hand pose estimation with object context
Non-parametric hand pose estimation with object context

Romero, J., Kjellström, H., Ek, C. H., Kragic, D.

Image and Vision Computing , 31(8):555 - 564, 2013 (article)

Abstract
In the spirit of recent work on contextual recognition and estimation, we present a method for estimating the pose of human hands, employing information about the shape of the object in the hand. Despite the fact that most applications of human hand tracking involve grasping and manipulation of objects, the majority of methods in the literature assume a free hand, isolated from the surrounding environment. Occlusion of the hand from grasped objects does in fact often pose a severe challenge to the estimation of hand pose. In the presented method, object occlusion is not only compensated for, it contributes to the pose estimation in a contextual fashion; this without an explicit model of object shape. Our hand tracking method is non-parametric, performing a nearest neighbor search in a large database (.. entries) of hand poses with and without grasped objects. The system that operates in real time, is robust to self occlusions, object occlusions and segmentation errors, and provides full hand pose reconstruction from monocular video. Temporal consistency in hand pose is taken into account, without explicitly tracking the hand in the high-dim pose space. Experiments show the non-parametric method to outperform other state of the art regression methods, while operating at a significantly lower computational cost than comparable model-based hand tracking methods.

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Publisher site pdf link (url) [BibTex]

Publisher site pdf link (url) [BibTex]

2012


Coupled Action Recognition and Pose Estimation from Multiple Views
Coupled Action Recognition and Pose Estimation from Multiple Views

Yao, A., Gall, J., van Gool, L.

International Journal of Computer Vision, 100(1):16-37, October 2012 (article)

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publisher's site code pdf Project Page Project Page Project Page [BibTex]

2012


publisher's site code pdf Project Page Project Page Project Page [BibTex]


{DRAPE: DRessing Any PErson}
DRAPE: DRessing Any PErson

Guan, P., Reiss, L., Hirshberg, D., Weiss, A., Black, M. J.

ACM Trans. on Graphics (Proc. SIGGRAPH), 31(4):35:1-35:10, July 2012 (article)

Abstract
We describe a complete system for animating realistic clothing on synthetic bodies of any shape and pose without manual intervention. The key component of the method is a model of clothing called DRAPE (DRessing Any PErson) that is learned from a physics-based simulation of clothing on bodies of different shapes and poses. The DRAPE model has the desirable property of "factoring" clothing deformations due to body shape from those due to pose variation. This factorization provides an approximation to the physical clothing deformation and greatly simplifies clothing synthesis. Given a parameterized model of the human body with known shape and pose parameters, we describe an algorithm that dresses the body with a garment that is customized to fit and possesses realistic wrinkles. DRAPE can be used to dress static bodies or animated sequences with a learned model of the cloth dynamics. Since the method is fully automated, it is appropriate for dressing large numbers of virtual characters of varying shape. The method is significantly more efficient than physical simulation.

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YouTube pdf talk Project Page Project Page [BibTex]

YouTube pdf talk Project Page Project Page [BibTex]


Visual Orientation and Directional Selectivity Through Thalamic Synchrony
Visual Orientation and Directional Selectivity Through Thalamic Synchrony

Stanley, G., Jin, J., Wang, Y., Desbordes, G., Wang, Q., Black, M., Alonso, J.

Journal of Neuroscience, 32(26):9073-9088, June 2012 (article)

Abstract
Thalamic neurons respond to visual scenes by generating synchronous spike trains on the timescale of 10–20 ms that are very effective at driving cortical targets. Here we demonstrate that this synchronous activity contains unexpectedly rich information about fundamental properties of visual stimuli. We report that the occurrence of synchronous firing of cat thalamic cells with highly overlapping receptive fields is strongly sensitive to the orientation and the direction of motion of the visual stimulus. We show that this stimulus selectivity is robust, remaining relatively unchanged under different contrasts and temporal frequencies (stimulus velocities). A computational analysis based on an integrate-and-fire model of the direct thalamic input to a layer 4 cortical cell reveals a strong correlation between the degree of thalamic synchrony and the nonlinear relationship between cortical membrane potential and the resultant firing rate. Together, these findings suggest a novel population code in the synchronous firing of neurons in the early visual pathway that could serve as the substrate for establishing cortical representations of the visual scene.

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preprint publisher's site Project Page [BibTex]

preprint publisher's site Project Page [BibTex]


Fourier-transform photocurrent spectroscopy using a supercontinuum light source
Fourier-transform photocurrent spectroscopy using a supercontinuum light source

Petermann, C., Beigang, R., Fischer, P.

APPLIED PHYSICS LETTERS, 100(6), 2012 (article)

Abstract
We demonstrate an implementation of frequency-encoded photocurrent spectroscopy using a super-continuum light source. The spectrally broad light is spatially dispersed and modulated with a special mechanical chopper design that permits a continuous wavelength-dependent modulation. After recombination, the light beam contains a frequency encoded spectrum which enables us to map the spectral response of a given sample in 60 ms and with a lateral resolution of 10 mu m. (C) 2012 American Institute of Physics.

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DOI [BibTex]

DOI [BibTex]


Eine neue Form von Cavity Enhanced Absorption Spectroscopy
Eine neue Form von Cavity Enhanced Absorption Spectroscopy

Petermann, C., Fischer, P.

DE Gruyter, 79(1), 2012, Best paper award OPTO 2011 (article)

Abstract
Wir stellen eine Kopplungsmethode für resonatorgestützte Absorptionsmessungen vor, bei der Licht durch einen im Resonator platzierten akustooptischen Modulator aktiv ein- und ausgekoppelt wird. Dies ermöglicht es Cavity-Ring-Down-Spektroskopie (CRDS) mit breitbandigen und zeitlich inkohärenten Lichtquellen niedriger spektraler Leistungsdichte durchzuführen. Das Verfahren wird zum ersten Mal mit einer breitbandigen Superkontinuum-Quelle demonstriert.

___________________________________________________________________________________________

A new coupling scheme for cavity enhanced absorption spectroscopy makes use of an intracavity acousto-optical modulator to actively switch light into (and out of) a resonator. This allows cavity ringdown spectroscopy (CRDS) to be implemented with broadband temporally incoherent light sources with low spectral power densities. The method is demonstrated for the first time using a broadband supercontinuum source. Best paper award OPTO 2011.

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link (url) [BibTex]

link (url) [BibTex]


An Introduction to Random Forests for Multi-class Object Detection
An Introduction to Random Forests for Multi-class Object Detection

Gall, J., Razavi, N., van Gool, L.

In Outdoor and Large-Scale Real-World Scene Analysis, 7474, pages: 243-263, LNCS, (Editors: Dellaert, Frank and Frahm, Jan-Michael and Pollefeys, Marc and Rosenhahn, Bodo and Leal-Taix’e, Laura), Springer, 2012 (incollection)

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code code for Hough forest publisher's site pdf Project Page [BibTex]

code code for Hough forest publisher's site pdf Project Page [BibTex]


Home {3D} body scans from noisy image and range data
Home 3D body scans from noisy image and range data

Weiss, A., Hirshberg, D., Black, M. J.

In Consumer Depth Cameras for Computer Vision: Research Topics and Applications, pages: 99-118, 6, (Editors: Andrea Fossati and Juergen Gall and Helmut Grabner and Xiaofeng Ren and Kurt Konolige), Springer-Verlag, 2012 (incollection)

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Project Page [BibTex]

Project Page [BibTex]

2005


Nonlinear optical spectroscopy of chiral molecules
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]

2005


DOI [BibTex]


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

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DOI [BibTex]

DOI [BibTex]

1998


Surface second-order nonlinear optical activity
Surface second-order nonlinear optical activity

Fischer, P., Buckingham, A.

JOURNAL OF THE OPTICAL SOCIETY OF AMERICA B-OPTICAL PHYSICS, 15(12):2951-2957, 1998 (article)

Abstract
Following the recent observation of a large second-harmonic intensity difference from a monolayer of chiral molecules with left and right circularly polarized light, the scattering theory is generalized and extended to predict linear and circular intensity differences for the more Versatile sum-frequency spectroscopy. Estimates indicate that intensity differences should be detectable for a typical experimental arrangement. The second-order nonlinear surface susceptibility tensor is given for different surface point groups in the electric dipole approximation; it is shown that nonlinear optical activity phenomena unambiguously probe molecular chirality only for molecular monolayers that are symmetric about the normal. Other surface symmetries can give rise to intensity differences from monolayers composed of achiral molecules. A water surface is predicted to show Linear and nonlinear optical activity in the presence of an electric field parallel to the surface. (C) 1998 Optical Society of America {[}S0740-3224(98)01311-3] OCIS codes: 190.0190, 190.4350, 240.6490.

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DOI [BibTex]

1998


DOI [BibTex]


Linear electro-optic effect in optically active liquids
Linear electro-optic effect in optically active liquids

Buckingham, A., Fischer, P.

CHEMICAL PHYSICS LETTERS, 297(3-4):239-246, 1998 (article)

Abstract
A linear effect of an electrostatic field F on the intensity of sum- and difference-frequency generation in a chiral liquid is predicted. It arises in the electric dipole approximation. The effect changes sign with the enantiomer and on reversing the direction of the electrostatic field. The sum-frequency generator chi(alpha beta gamma)((2)) (-omega(3);omega(1),omega(2)), where omega(3) = omega(1) + omega(2), and the electric field-induced sum-frequency generator chi(alpha beta gamma delta)((3))(-omega(3);omega(1),omega(2),0)F-delta interfere and their contributions to the scattering power can be distinguished. Encouraging predictions are given for a typical experimental arrangement. (C) 1998 Elsevier Science B.V. All rights reserved.

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DOI [BibTex]

DOI [BibTex]


Monolayers of hexadecyltrimethylammonium p-tosylate at the air-water interface. 1. Sum-frequency spectroscopy
Monolayers of hexadecyltrimethylammonium p-tosylate at the air-water interface. 1. Sum-frequency spectroscopy

Bell, G., Li, Z., Bain, C., Fischer, P., Duffy, D.

JOURNAL OF PHYSICAL CHEMISTRY B, 102(47):9461-9472, 1998 (article)

Abstract
Sum-frequency vibrational spectroscopy has been used to determine the structure of monolayers of the cationic surfactant, hexadecyltrimethylammonium p-tosylate (C(16)TA(+)Ts(-)), at the surface of water. Selective deuteration of the cation or the anion allowed the separate detection of sum-frequency spectra of the surfactant and of counterions that are bound to the monolayer. The p-tosylate ions an oriented with their methyl groups pointing away from the aqueous subphase and with the C-2 axis tilted, on average, by 30-40 degrees from the surface normal. The vibrational spectra of C(16)TA(+) indicate that the number of gauche defects in the monolayer does not change dramatically when bromide counterions are replaced by p-tosylate. The ends of the hydrocarbon chains of C16TA+ are, however, tilted much further from the surface normal in the presence of p-tosylate than in the presence of bromide. A quantitative analysis of the sum-frequency spectra requires a knowledge of the molecular hyperpolarizability tensor: the role of ab initio calculations and Raman spectroscopy in determining the components of this tensor is discussed.

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DOI [BibTex]

DOI [BibTex]


Ultraviolet resonance Raman study of drug binding in dihydrofolate reductase, gyrase, and catechol O-methyltransferase
Ultraviolet resonance Raman study of drug binding in dihydrofolate reductase, gyrase, and catechol O-methyltransferase

Couling, V., Fischer, P., Klenerman, D., Huber, W.

BIOPHYSICAL JOURNAL, 75(2):1097-1106, 1998 (article)

Abstract
This paper presents a study of the use of ultraviolet resonance Raman (UVRR) spectroscopic methods as a means of elucidating aspects of drug-protein interactions. Some of the RR vibrational bands of the aromatic amino acids tyrosine and tryptophan are sensitive to the microenvironment, and the use of UV excitation radiation allows selective enhancement of the spectral features of the aromatic amino acids, enabling observation specifically of their change in microenvironment upon drug binding. The three drug-protein systems investigated in this study are dihydrofolate reductase with its inhibitor trimethoprim, gyrase with novobiocin, and catechol O-methyltransferase with dinitrocatechol. It is demonstrated that UVRR spectroscopy has adequate sensitivity to be a useful means of detecting drug-protein interactions in those systems for which the electronic absorption of the aromatic amino acids changes because of hydrogen bonding and/or possible dipole-dipole and dipole-polarizability interactions with the ligand.

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DOI [BibTex]

DOI [BibTex]