Design and Control of an Anthropomorphic Robotic Finger with Multi-point Tactile Sensation

The goal of this research is to develop the prototype of a tactile sensing platform for anthropomorphic manipulation research. We investigate this problem through the fabrication and simple control of a planar 2-DOF robotic finger inspired by anatomic consistency, self-containment, and adaptability. The robot is equipped with a tactile sensor array based on optical transducer technology whereby localized changes in light intensity within an illuminated foam substrate correspond to the distribution and magnitude of forces applied to the sensor surface plane. The integration of tactile perception is a key component in realizing robotic systems which organically interact with the world. Such natural behavior is characterized by compliant performance that can initiate internal, and respond to external, force application in a dynamic environment. However, most of the current manipulators that support some form of haptic feedback either solely derive proprioceptive sensation or only limit tactile sensors to the mechanical fingertips. These constraints are due to the technological challenges involved in high resolution, multi-point tactile perception. In this work, however, we take the opposite approach, emphasizing the role of full-finger tactile feedback in the refinement of manual capabilities. To this end, we propose and implement a control framework for sensorimotor coordination analogous to infant-level grasping and fixturing reflexes. This thesis details the mechanisms used to achieve these sensory, actuation, and control objectives, along with the design philosophies and biological influences behind them. The results of behavioral experiments with a simple tactilely-modulated control scheme are also described. The hope is to integrate the modular finger into an %engineered analog of the human hand with a complete haptic system.

On Degeneracy of Linear Reconstruction from Three Views: Linear Line Complex and Applications

This paper investigates the linear degeneracies of projective structure estimation from point and line features across three views. We show that the rank of the linear system of equations for recovering the trilinear tensor of three views reduces to 23 (instead of 26) in the case when the scene is a Linear Line Complex (set of lines in space intersecting at a common line) and is 21 when the scene is planar. The LLC situation is only linearly degenerate, and we show that one can obtain a unique solution when the admissibility constraints of the tensor are accounted for. The line configuration described by an LLC, rather than being some obscure case, is in fact quite typical. It includes, as a particular example, the case of a camera moving down a hallway in an office environment or down an urban street. Furthermore, an LLC situation may occur as an artifact such as in direct estimation from spatio-temporal derivatives of image brightness. Therefore, an investigation into degeneracies and their remedy is important also in practice.

Systematic study of the static electrical properties of the CO molecule: influence of the basis set size and correlation energy

The influence of the basis set size and the correlation energy in the static electrical properties of the CO molecule is assessed. In particular, we have studied both the nuclear relaxation and the vibrational contributions to the static molecular electrical properties, the vibrational Stark effect (VSE) and the vibrational intensity effect (VIE). From a mathematical point of view, when a static and uniform electric field is applied to a molecule, the energy of this system can be expressed in terms of a double power series with respect to the bond length and to the field strength. From the power series expansion of the potential energy, field-dependent expressions for the equilibrium geometry, for the potential energy and for the force constant are obtained. The nuclear relaxation and vibrational contributions to the molecular electrical properties are analyzed in terms of the derivatives of the electronic molecular properties. In general, the results presented show that accurate inclusion of the correlation energy and large basis sets are needed to calculate the molecular electrical properties and their derivatives with respect to either nuclear displacements or/and field strength. With respect to experimental data, the calculated power series coefficients are overestimated by the SCF, CISD, and QCISD methods. On the contrary, perturbation methods (MP2 and MP4) tend to underestimate them. In average and using the 6-311 + G(3df) basis set and for the CO molecule, the nuclear relaxation and the vibrational contributions to the molecular electrical properties amount to 11.7%, 3.3%, and 69.7% of the purely electronic μ, α, and β values, respectively

C-H···O H-bonded complexes: how does basis set superposition error change their potential-energy surfaces?

Geometries, vibrational frequencies, and interaction energies of the CNH⋯O3 and HCCH⋯O3 complexes are calculated in a counterpoise-corrected (CP-corrected) potential-energy surface (PES) that corrects for the basis set superposition error (BSSE). Ab initio calculations are performed at the Hartree-Fock (HF) and second-order Møller-Plesset (MP2) levels, using the 6-31G(d,p) and D95++(d,p) basis sets. Interaction energies are presented including corrections for zero-point vibrational energy (ZPVE) and thermal correction to enthalpy at 298 K. The CP-corrected and conventional PES are compared; the unconnected PES obtained using the larger basis set including diffuse functions exhibits a double well shape, whereas use of the 6-31G(d,p) basis set leads to a flat single-well profile. The CP-corrected PES has always a multiple-well shape. In particular, it is shown that the CP-corrected PES using the smaller basis set is qualitatively analogous to that obtained with the larger basis sets, so the CP method becomes useful to correctly describe large systems, where the use of small basis sets may be necessary

A quantum molecular similarity analysis of changes in molecular electron density caused by basis set flotation and electric field application

Quantum molecular similarity (QMS) techniques are used to assess the response of the electron density of various small molecules to application of a static, uniform electric field. Likewise, QMS is used to analyze the changes in electron density generated by the process of floating a basis set. The results obtained show an interrelation between the floating process, the optimum geometry, and the presence of an external field. Cases involving the Le Chatelier principle are discussed, and an insight on the changes of bond critical point properties, self-similarity values and density differences is performed

How does basis set superposition error change the potential surfaces for hydrogen-bonded dimers?

We describe a simple method to automate the geometric optimization of molecular orbital calculations of supermolecules on potential surfaces that are corrected for basis set superposition error using the counterpoise (CP) method. This method is applied to the H-bonding complexes HF/HCN, HF/H2O, and HCCH/H2O using the 6-31G(d,p) and D95 + + (d,p) basis sets at both the Hartree-Fock and second-order Møller-Plesset levels. We report the interaction energies, geometries, and vibrational frequencies of these complexes on the CP-optimized surfaces; and compare them with similar values calculated using traditional methods, including the (more traditional) single point CP correction. Upon optimization on the CP-corrected surface, the interaction energies become more negative (before vibrational corrections) and the H-bonding stretching vibrations decrease in all cases. The extent of the effects vary from extremely small to quite large depending on the complex and the calculational method. The relative magnitudes of the vibrational corrections cannot be predicted from the H-bond stretching frequencies alone

Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory, fourth-order Møller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+ 1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values

Basis set superposition error effects, excited-state potential energy surface and photodynamics of thymine

En aquesta tesi he estudiat l'efecte de l'error de superposició de base (BSSE) en la planaritat d'algunes molècules. He observat que l'ús d'alguns mètodes de càlcul amb determinades funcions de base descriuen mínims d'energia no planars per les bases nitrogenades de l'ADN. He demostrat que aquests problemes es poden arreglar utilitzant el mètode Counterpoise per corregir el BSSE en els càlculs. En aquesta tesi també he estudiat la fotofísica de la timina i els resultats mostren que existeixen dos camins de relaxació des de l'estat excitat que permeten la regeneració de l'estructura inicial de forma ultraràpida.

Implementation and application of basis set superposition error-correction schemes to the theoretical modeling of weak intermolecular interactions

This thesis deals with the so-called Basis Set Superposition Error (BSSE) from both a methodological and a practical point of view. The purpose of the present thesis is twofold: (a) to contribute step ahead in the correct characterization of weakly bound complexes and, (b) to shed light the understanding of the actual implications of the basis set extension effects in the ab intio calculations and contribute to the BSSE debate. The existing BSSE-correction procedures are deeply analyzed, compared, validated and, if necessary, improved. A new interpretation of the counterpoise (CP) method is used in order to define counterpoise-corrected descriptions of the molecular complexes. This novel point of view allows for a study of the BSSE-effects not only in the interaction energy but also on the potential energy surface and, in general, in any property derived from the molecular energy and its derivatives A program has been developed for the calculation of CP-corrected geometry optimizations and vibrational frequencies, also using several counterpoise schemes for the case of molecular clusters. The method has also been implemented in Gaussian98 revA10 package. The Chemical Hamiltonian Approach (CHA) methodology has been also implemented at the RHF and UHF levels of theory for an arbitrary number interacting systems using an algorithm based on block-diagonal matrices. Along with the methodological development, the effects of the BSSE on the properties of molecular complexes have been discussed in detail. The CP and CHA methodologies are used for the determination of BSSE-corrected molecular complexes properties related to the Potential Energy Surfaces and molecular wavefunction, respectively. First, the behaviour of both BSSE-correction schemes are systematically compared at different levels of theory and basis sets for a number of hydrogen-bonded complexes. The Complete Basis Set (CBS) limit of both uncorrected and CP-corrected molecular properties like stabilization energies and intermolecular distances has also been determined, showing the capital importance of the BSSE correction. Several controversial topics of the BSSE correction are addressed as well. The application of the counterpoise method is applied to internal rotational barriers. The importance of the nuclear relaxation term is also pointed out. The viability of the CP method for dealing with charged complexes and the BSSE effects on the double-well PES blue-shifted hydrogen bonds is also studied in detail. In the case of the molecular clusters the effect of high-order BSSE effects introduced with the hierarchical counterpoise scheme is also determined. The effect of the BSSE on the electron density-related properties is also addressed. The first-order electron density obtained with the CHA/F and CHA/DFT methodologies was used to assess, both graphically and numerically, the redistribution of the charge density upon BSSE-correction. Several tools like the Atoms in Molecules topologycal analysis, density difference maps, Quantum Molecular Similarity, and Chemical Energy Component Analysis were used to deeply analyze, for the first time, the BSSE effects on the electron density of several hydrogen bonded complexes of increasing size. The indirect effect of the BSSE on intermolecular perturbation theory results is also pointed out It is shown that for a BSSE-free SAPT study of hydrogen fluoride clusters, the use of a counterpoise-corrected PES is essential in order to determine the proper molecular geometry to perform the SAPT analysis.

A proposal to estimate the motion of an underwater vehicle through visual mosaicking

This thesis proposes a solution to the problem of estimating the motion of an Unmanned Underwater Vehicle (UUV). Our approach is based on the integration of the incremental measurements which are provided by a vision system. When the vehicle is close to the underwater terrain, it constructs a visual map (so called "mosaic") of the area where the mission takes place while, at the same time, it localizes itself on this map, following the Concurrent Mapping and Localization strategy. The proposed methodology to achieve this goal is based on a feature-based mosaicking algorithm. A down-looking camera is attached to the underwater vehicle. As the vehicle moves, a sequence of images of the sea-floor is acquired by the camera. For every image of the sequence, a set of characteristic features is detected by means of a corner detector. Then, their correspondences are found in the next image of the sequence. Solving the correspondence problem in an accurate and reliable way is a difficult task in computer vision. We consider different alternatives to solve this problem by introducing a detailed analysis of the textural characteristics of the image. This is done in two phases: first comparing different texture operators individually, and next selecting those that best characterize the point/matching pair and using them together to obtain a more robust characterization. Various alternatives are also studied to merge the information provided by the individual texture operators. Finally, the best approach in terms of robustness and efficiency is proposed. After the correspondences have been solved, for every pair of consecutive images we obtain a list of image features in the first image and their matchings in the next frame. Our aim is now to recover the apparent motion of the camera from these features. Although an accurate texture analysis is devoted to the matching pro-cedure, some false matches (known as outliers) could still appear among the right correspon-dences. For this reason, a robust estimation technique is used to estimate the planar transformation (homography) which explains the dominant motion of the image. Next, this homography is used to warp the processed image to the common mosaic frame, constructing a composite image formed by every frame of the sequence. With the aim of estimating the position of the vehicle as the mosaic is being constructed, the 3D motion of the vehicle can be computed from the measurements obtained by a sonar altimeter and the incremental motion computed from the homography. Unfortunately, as the mosaic increases in size, image local alignment errors increase the inaccuracies associated to the position of the vehicle. Occasionally, the trajectory described by the vehicle may cross over itself. In this situation new information is available, and the system can readjust the position estimates. Our proposal consists not only in localizing the vehicle, but also in readjusting the trajectory described by the vehicle when crossover information is obtained. This is achieved by implementing an Augmented State Kalman Filter (ASKF). Kalman filtering appears as an adequate framework to deal with position estimates and their associated covariances. Finally, some experimental results are shown. A laboratory setup has been used to analyze and evaluate the accuracy of the mosaicking system. This setup enables a quantitative measurement of the accumulated errors of the mosaics created in the lab. Then, the results obtained from real sea trials using the URIS underwater vehicle are shown.

Realizability of Point Processes

There are various situations in which it is natural to ask whether a given collection of k functions, ρ j (r 1,…,r j ), j=1,…,k, defined on a set X, are the first k correlation functions of a point process on X. Here we describe some necessary and sufficient conditions on the ρ j ’s for this to be true. Our primary examples are X=ℝ d , X=ℤ d , and X an arbitrary finite set. In particular, we extend a result by Ambartzumian and Sukiasian showing realizability at sufficiently small densities ρ 1(r). Typically if any realizing process exists there will be many (even an uncountable number); in this case we prove, when X is a finite set, the existence of a realizing Gibbs measure with k body potentials which maximizes the entropy among all realizing measures. We also investigate in detail a simple example in which a uniform density ρ and translation invariant ρ 2 are specified on ℤ; there is a gap between our best upper bound on possible values of ρ and the largest ρ for which realizability can be established.

Calibrating flood inundation models: identifying and addressing uncertainty in satellite observed flood extents

Improvements in the resolution of satellite imagery have enabled extraction of water surface elevations at the margins of the flood. Comparison between modelled and observed water surface elevations provides a new means for calibrating and validating flood inundation models, however the uncertainty in this observed data has yet to be addressed. Here a flood inundation model is calibrated using a probabilistic treatment of the observed data. A LiDAR guided snake algorithm is used to determine an outline of a flood event in 2006 on the River Dee, North Wales, UK, using a 12.5m ERS-1 image. Points at approximately 100m intervals along this outline are selected, and the water surface elevation recorded as the LiDAR DEM elevation at each point. With a planar water surface from the gauged upstream to downstream water elevations as an approximation, the water surface elevations at points along this flooded extent are compared to their ‘expected’ value. The pattern of errors between the two show a roughly normal distribution, however when plotted against coordinates there is obvious spatial autocorrelation. The source of this spatial dependency is investigated by comparing errors to the slope gradient and aspect of the LiDAR DEM. A LISFLOOD-FP model of the flood event is set-up to investigate the effect of observed data uncertainty on the calibration of flood inundation models. Multiple simulations are run using different combinations of friction parameters, from which the optimum parameter set will be selected. For each simulation a T-test is used to quantify the fit between modelled and observed water surface elevations. The points chosen for use in this T-test are selected based on their error. The criteria for selection enables evaluation of the sensitivity of the choice of optimum parameter set to uncertainty in the observed data. This work explores the observed data in detail and highlights possible causes of error. The identification of significant error (RMSE = 0.8m) between approximate expected and actual observed elevations from the remotely sensed data emphasises the limitations of using this data in a deterministic manner within the calibration process. These limitations are addressed by developing a new probabilistic approach to using the observed data.

Case study: object and ground point separation on a river bank using airborne based LIDAR data

In the past decade, airborne based LIght Detection And Ranging (LIDAR) has been recognised by both the commercial and public sectors as a reliable and accurate source for land surveying in environmental, engineering and civil applications. Commonly, the first task to investigate LIDAR point clouds is to separate ground and object points. Skewness Balancing has been proven to be an efficient non-parametric unsupervised classification algorithm to address this challenge. Initially developed for moderate terrain, this algorithm needs to be adapted to handle sloped terrain. This paper addresses the difficulty of object and ground point separation in LIDAR data in hilly terrain. A case study on a diverse LIDAR data set in terms of data provider, resolution and LIDAR echo has been carried out. Several sites in urban and rural areas with man-made structure and vegetation in moderate and hilly terrain have been investigated and three categories have been identified. A deeper investigation on an urban scene with a river bank has been selected to extend the existing algorithm. The results show that an iterative use of Skewness Balancing is suitable for sloped terrain.

Strongly nucleophilic RhI centre in square-planar complexes with terdentate (κ3) 2,2′:6′,2′′-terpyridine ligands: crystallographic, electrochemical and density functional theoretical studies

Rh-I-terpyridine complexes have been unambiguously formed for the first time. The 2,21:6',2"-terpyridine (tpy), 4'-chloro-2,2':6',2"-terpyridine (4'-Cl-tpy) and 4'-(tert-butyldimethylsilyl-ortho-carboranyl)-2,2':6',2"-terpyridine (carboranyl-tpy) ligands were used for successful syntheses and characterisation of the corresponding Rh-I complexes with halide coligands, [Rh(X)(4'-Y-terpyridine)] (X = Cl, Y = H, Cl, carboranyl; X = Br, Y = H). All four neutral Rh-tpy complexes are square planar, with Rh-X bonds in the plane of the 4'-Y-terpyridine ligands. Full characterisation of these dark blue, highly air-sensitive compounds was hampered by their poor solubility in various organic solvents. This is mainly due to the formation of pi-stacked aggregates, as evidenced by the crystal structure of [Rh(Cl)(tpy)]; in addition, [Rh(Cl)(carboranyl-tpy)] merely forms discrete dimers. The (bonding) properties of the novel Rh-I-terpyridine complexes have been studied with single-crystal X-ray diffraction, (time-dependent) density functional theoretical (DFT) calculations, far-infrared spectroscopy, electronic absorption spectroscopy and cyclic voltammetry. From DFT calculations, the HOMO of the studied Rh-I-terpyridine complexes involves predominantly the metal centre, while the LUMO resides on the terpyridine ligand. Absorption bands of the studied complexes in the visible region (400-900 nm) can be assigned to MLCT and MLCT/XLCT transitions. The relatively low oxidation potentials of [Rh(X)(tpy)] (X = Cl, Br) point to a high electron density on the metal centre. This makes the Rh-I-terpyridine complexes strongly nucleophilic and (potentially) highly reactive towards various (small) substrate molecules containing carbon-halide bonds.

Ultraconserved words point to deep language ancestry across Eurasia

The search for ever deeper relationships among the World’s languages is bedeviled by the fact that most words evolve too rapidly to preserve evidence of their ancestry beyond 5,000 to 9,000 y. On the other hand, quantitative modeling indicates that some “ultraconserved” words exist that might be used to find evidence for deep linguistic relationships beyond that time barrier. Here we use a statistical model, which takes into account the frequency with which words are used in common everyday speech, to predict the existence of a set of such highly conserved words among seven language families of Eurasia postulated to form a linguistic superfamily that evolved from a common ancestor around 15,000 y ago. We derive a dated phylogenetic tree of this proposed superfamily with a time-depth of ∼14,450 y, implying that some frequently used words have been retained in related forms since the end of the last ice age. Words used more than once per 1,000 in everyday speech were 7- to 10-times more likely to show deep ancestry on this tree. Our results suggest a remarkable fidelity in the transmission of some words and give theoretical justification to the search for features of language that might be preserved across wide spans of time and geography.