Robust fitting for generalized additive models for location, scale and shape

The validity of estimation and smoothing parameter selection for the wide class of generalized additive models for location, scale and shape (GAMLSS) relies on the correct specification of a likelihood function. Deviations from such assumption are known to mislead any likelihood-based inference and can hinder penalization schemes meant to ensure some degree of smoothness for nonlinear effects. We propose a general approach to achieve robustness in fitting GAMLSSs by limiting the contribution of observations with low log-likelihood values. Robust selection of the smoothing parameters can be carried out either by minimizing information criteria that naturally arise from the robustified likelihood or via an extended Fellner–Schall method. The latter allows for automatic smoothing parameter selection and is particularly advantageous in applications with multiple smoothing parameters. We also address the challenge of tuning robust estimators for models with nonlinear effects by proposing a novel median downweighting proportion criterion. This enables a fair comparison with existing robust estimators for the special case of generalized additive models, where our estimator competes favorably. The overall good performance of our proposal is illustrated by further simulations in the GAMLSS setting and by an application to functional magnetic resonance brain imaging using bivariate smoothing splines

Quantum-kinetic theory of photocurrent generation via direct and phonon-mediated optical transitions

A quantum-kinetic theory of direct and phonon mediated indirect optical transitions is developed within the framework of the non-equilibrium Green's function formalism. After validation against the standard Fermi-Golden-Rule approach in the bulk case, it is used in the simulation of photocurrent generation in ultra-thin crystalline silicon p-i-n-junction devices.Comment: 12 pages, 11 figure

Microscopic non-equilibrium theory of quantum well solar cells

We present a microscopic theory of bipolar quantum well structures in the photovoltaic regime, based on the non-equilibrium Green's function formalism for a multi band tight binding Hamiltonian. The quantum kinetic equations for the single particle Green's functions of electrons and holes are self-consistently coupled to Poisson's equation, including inter-carrier scattering on the Hartree level. Relaxation and broadening mechanisms are considered by the inclusion of acoustic and optical electron-phonon interaction in a self consistent Born approximation of the scattering self energies. Photogeneration of carriers is described on the same level in terms of a self energy derived from the standard dipole approximation of the electron-photon interaction. Results from a simple two band model are shown for the local density of states, spectral response, current spectrum, and current-voltage characteristics for generic single quantum well systems.Comment: 10 pages, 6 figures; corrected typos, changed caption Fig. 1, replaced Fig.

Robust Fitting for Generalized Additive Models for Location, Scale and Shape

The validity of estimation and smoothing parameter selection for the wide class of generalized additive models for location, scale and shape (GAMLSS) relies on the correct specification of a likelihood function. Deviations from such assumption are known to mislead any likelihood-based inference and can hinder penalization schemes meant to ensure some degree of smoothness for non-linear effects. We propose a general approach to achieve robustness in fitting GAMLSSs by limiting the contribution of observations with low log-likelihood values. Robust selection of the smoothing parameters can be carried out either by minimizing information criteria that naturally arise from the robustified likelihood or via an extended Fellner-Schall method. The latter allows for automatic smoothing parameter selection and is particularly advantageous in applications with multiple smoothing parameters. We also address the challenge of tuning robust estimators for models with non-linear effects by proposing a novel median downweighting proportion criterion. This enables a fair comparison with existing robust estimators for the special case of generalized additive models, where our estimator competes favorably. The overall good performance of our proposal is illustrated by further simulations in the GAMLSS setting and by an application to functional magnetic resonance brain imaging using bivariate smoothing splines

Theory and simulation of photogeneration and transport in Si-SiOx superlattice absorbers

Si-SiOx superlattices are among the candidates that have been proposed as high band gap absorber material in all-Si tandem solar cell devices. Owing to the large potential barriers for photoexited charge carriers, transport in these devices is restricted to quantum-confined superlattice states. As a consequence of the finite number of wells and large built-in fields, the electronic spectrum can deviate considerably from the minibands of a regular superlattice. In this article, a quantum-kinetic theory based on the non-equilibrium Green's function formalism for an effective mass Hamiltonian is used for investigating photogeneration and transport in such devices for arbitrary geometry and operating conditions. By including the coupling of electrons to both photons and phonons, the theory is able to provide a microscopic picture of indirect generation, carrier relaxation, and inter-well transport mechanisms beyond the ballistic regime

Theory and simulation of quantum photovoltaic devices based on the non-equilibrium Green's function formalism

This article reviews the application of the non-equilibrium Green's function formalism to the simulation of novel photovoltaic devices utilizing quantum confinement effects in low dimensional absorber structures. It covers well-known aspects of the fundamental NEGF theory for a system of interacting electrons, photons and phonons with relevance for the simulation of optoelectronic devices and introduces at the same time new approaches to the theoretical description of the elementary processes of photovoltaic device operation, such as photogeneration via coherent excitonic absorption, phonon-mediated indirect optical transitions or non-radiative recombination via defect states. While the description of the theoretical framework is kept as general as possible, two specific prototypical quantum photovoltaic devices, a single quantum well photodiode and a silicon-oxide based superlattice absorber, are used to illustrated the kind of unique insight that numerical simulations based on the theory are able to provide.Comment: 20 pages, 10 figures; invited review pape

Efficient decellularization of equine tendon with preserved biomechanical properties and cytocompatibility for human tendon surgery indications.

Chronic and acute tendon injuries are frequent afflictions, for which treatment is often long and unsatisfactory. When facing extended injuries, matrices and scaffolds with sufficient biomechanical properties are required for surgical repair and could additionally serve as supports for cellular therapies to improve healing. In this study, protocols of either commonly used detergents only (SDS 1%, Triton 1%, TBP 1%, and Tween-20 1%) or a combination of freeze/thaw (F/T) cycles with decellularization agents (NaCl 1M, ddH <sub>2</sub> O) were evaluated for the decellularization of horse equine superficial digital flexor tendon (SDFT) for hand flexor or extensor tendon reconstruction. Decellularization efficiency was assessed microscopically by histological staining (HE, DAPI) and DNA quantification. Macroscopical structure and biomechanical integrity of the tendon matrices were further assessed by gross observation, histological staining (SR), and mechanical testing (ultimate strain and stress, Young's modulus, energy to failure) for select protocols. Decellularization with hypertonic NaCl 1M in association with F/T cycles produced the most robust tendon matrices, which were nontoxic after 10 days for subsequent recellularization with human fetal progenitor tendon cells (hFPTs). This standardized protocol uses a less aggressive decellularization agent than current practice, which allows subsequent reseeding with allogenic cells, therefore making them very suitable and bioengineered tendon matrices for human tendon reconstruction in the clinic

SU(2) symmetry in a Hubbard model with spin-orbit coupling

We study the underlying symmetry in a spin-orbit coupled tight-binding model with Hubbard interaction. It is shown that, in the absence of the on-site interaction, the system possesses the SU(2) symmetry arising from the timereversal symmetry. The influence of the on-site interaction on the symmetry depends on the topology of the networks: The SU(2) symmetry is shown to be the spin rotation symmetry of a simply-connected lattice, so it still holds in the presence of the Hubbard correlation. In contrary, the on-site interaction breaks the SU(2) symmetry of a multi-connected lattice.Comment: 5 pages, 2 figure

The Alkaline Hydrolysis of Sulfonate Esters: Challenges in Interpreting Experimental and Theoretical Data

Sulfonate ester hydrolysis has been the subject of recent debate, with experimental evidence interpreted in terms of both stepwise and concerted mechanisms. In particular, a recent study of the alkaline hydrolysis of a series of benzene arylsulfonates (Babtie et al., Org. Biomol. Chem. 10, 2012, 8095) presented a nonlinear Brønsted plot, which was explained in terms of a change from a stepwise mechanism involving a pentavalent intermediate for poorer leaving groups to a fully concerted mechanism for good leaving groups and supported by a theoretical study. In the present work, we have performed a detailed computational study of the hydrolysis of these compounds and find no computational evidence for a thermodynamically stable intermediate for any of these compounds. Additionally, we have extended the experimental data to include pyridine-3-yl benzene sulfonate and its N-oxide and N-methylpyridinium derivatives. Inclusion of these compounds converts the Brønsted plot to a moderately scattered but linear correlation and gives a very good Hammett correlation. These data suggest a concerted pathway for this reaction that proceeds via an early transition state with little bond cleavage to the leaving group, highlighting the care that needs to be taken with the interpretation of experimental and especially theoretical data