Cellulose pyrolysis and quantum chemistry

Cellulose is the major constituent of most plants of interest as renewable sources of energy and is the most extensively studied form of biomass or biomass constituent. Predicting the mass loss and product yields when cellulose is subjected to increased temperature represents a fundamental problem in the thermal release of biomass energy. Unfortunately, at this time, there is no internally consistent model of cellulose pyrolysis that can organize the varied experimental data now available or provide a guide for additional experiments. Here, we present a model of direct cellulose pyrolysis using a multistage decay scheme that we first presented in the IJQC in 1984. This decay scheme can, with the help of an inverse method of assigning reaction rates, provide a reasonable account of the direct fast pyrolysis yield measurements. The model is suggestive of dissociation states of d-glucose (C6H10O5,), the fundamental cellulose monomer. The model raises the question as to whether quantum chemistry could now provide the dissociation energies for the principal breakup modes of glucose into C-1, C-2, C-3, C-4, and C-5 compounds. These calculations would help in achieving a more fundamental description of volatile generation from cellulose pyrolysis and could serve as a guide for treating hemicellulose and lignin, the other major biomass constituents. Such advances could lead to the development of a predictive science of biomass pyrolysis that would facilitate the design of liquifiers and gasifiers based upon renewable feedstocks. (C) 1998 John Wiley & Sons, Inc.

Orthogonality criterion for banishing hydrino states from standard quantum mechanics

Orthogonality criterion is used to show in a very simple and general way that anomalous bound-state solutions for the Coulomb potential (hydrino states) do not exist as bona fide solutions of the Schrodinger, Klein-Gordon and Dirac equations. (C) 2007 Elsevier B.V. All rights reserved.

Extension of PT-symmetric quantum mechanics to the Dirac theory with position-dependent mass

We present a new method to construct the exactly solvable PT-symmetric potentials within the framework of the position-dependent effective mass Dirac equation with the vector potential coupling scheme in 1 + 1 dimensions. In order to illustrate the procedure, we produce three PT-symmetric potentials as examples, which are PT-symmetric harmonic oscillator-like potential, PT-symmetric potential with the form of a linear potential plus an inversely linear potential, and PT-symmetric kink-like potential, respectively. The real relativistic energy levels and corresponding spinor components for the bound states are obtained by using the basic concepts of the supersymmetric quantum mechanics formalism and function analysis method. (C) 2007 Elsevier B.V. All rights reserved.

Estudo de titanatos nanoestruturados obtidos por tratamento hidrotérmico de óxido de titânio em meio alcalino

TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800ºC), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7·nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200ºC, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400ºC. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150ºC, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase

Magnetoresistance and transistor-like behavior of a double quantum-dot via crossed Andreev reflections

The electric current and the magnetoresistance effect are studied in a double quantum-dot system, where one of the dots QD(a) is coupled to two ferromagnetic electrodes (F-1; F-2), while the second QD(b) is connected to a superconductor S. For energy scales within the superconductor gap, electric conduction is allowed by Andreev reflection processes. Due to the presence of two ferromagnetic leads, non-local crossed Andreev reflections are possible. We found that the magnetoresistance sign can be changed by tuning the external potential applied to the ferromagnets. In addition, it is possible to control the current of the first ferromagnet (F-1) through the potential applied to the second one (F-2). We have also included intradot interaction and gate voltages at each quantum dot and analyzed their influence through a mean field approximation. The interaction reduces the current amplitudes with respect to the non-interacting case, but the switching effect still remains as a manifestation of quantum coherence, in scales of the order of the superconductor coherence length. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4723000]

Nonlinear Lattice Within Supersymmetric Quantum Mechanics Formalism

In the last decades, the study of nonlinear one dimensional lattices has attracted much attention of the scientific community. One of these lattices is related to a simplified model for the DNA molecule, allowing to recover experimental results, such as the denaturation of DNA double helix. Inspired by this model we construct a Hamiltonian for a reflectionless potential through the Supersymmetric Quantum Mechanics formalism, SQM. Thermodynamical properties of such one dimensional lattice are evaluated aming possible biological applications.

Equivalence of many-photon Green's functions in the Duffin-Kemmer-Petiau and Klein-Gordon-Fock statistical quantum field theories

Using the functional integral formalism for the statistical generating functional in the statistical (finite temperature) quantum field theory, we prove the equivalence of many-photon Greens functions in the Duffin-Kennner-Petiau and Klein-Gordon-Fock statistical quantum field theories. As an illustration, we calculate the one-loop polarization operators in both theories and demonstrate their coincidence.

Quantum coherent tunneling between two atomic-molecular Bose-Einstein condensates

We study the quantum coherent tunneling dynamics of two weakly coupled atomic-molecular Bose-Einstein condensates (AMBEC). A weak link is supposed to be provided by a double-well trap. The regions of parameters where the macroscopic quantum localization of the relative atomic population occurs are revealed. The different dynamical regimes are found depending on the value of nonlinearity, namely, coupled oscillations of population imbalance of atomic and molecular condensate, including irregular oscillations regions, and macroscopic quantum self trapping regimes. Quantum means and quadrature variances are calculated for population of atomic and molecular condensates and the possibility of quadrature squeezing is shown via stochastic simulations within P-positive phase space representation method. Linear tunnel coupling between two AMBEC leads to correlations in quantum statistics.

Combinatorial identities and quantum state densities of supersymmetric sigma models on N-folds

There is a remarkable connection between the number of quantum states of conformal theories and the sequence of dimensions of Lie algebras. In this paper, we explore this connection by computing the asymptotic expansion of the elliptic genus and the microscopic entropy of black holes associated with (supersymmetric) sigma models. The new features of these results are the appearance of correct prefactors in the state density expansion and in the coefficient of the logarithmic correction to the entropy.

Momentum-space non-hydrogenic wavefunction of quantum defect theory

We derive a closed-form analytic expression in momentum space for the asymptotic non-hydrogenic wavefunction of the quantum defect theory (QDT) due to Seaton and compare it with a widely used QDT-approximate wavefunction for the Rydberg states Li-3(2s), Mg-24(6s) and Rb-37(5s).

Quantum description of spin tunneling in magnetic molecules

Starting from a phenomenological Hamiltonian originally written in terms of angular momentum operators we derive a new quantum angle-based Hamiltonian that allows for a discussion on the quantum spin tunneling. The study of the applicability of the present approach, carried out in calculations with a soluble quasi-spin model, shows that we are allowed to use our method in the description of physical systems such as the Mn12-acetate molecule, as well as the octanuclear iron cluster, Fe8, in a reliable way. With the present description the interpretation of the spin tunneling is seen to be direct, the spectra and energy barriers of those systems are obtained, and it is shown that they agree with the experimental ones. (c) 2006 Elsevier B.V. All rights reserved.

Nonequilibrium dynamics of quantum fields

The nonequilibrium effective equation of motion for a scalar background field in a thermal bath is studied numerically. This equation emerges from a microscopic quantum field theory derivation and it is suitable to a Langevin simulation on the lattice. Results for both the symmetric and broken phases are presented.

Quantization rules for bound states in quantum wells

An algebraic reformulation of the Bohr-Sommerfeld (BS) quantization rule is suggested and applied to the study of bound states in one-dimensional quantum wells. The energies obtained with the present quantization rule are compared to those obtained with the usual BS and WKB quantization rules and with the exact solution of the Schrodinger equation. We find that, in diverse cases of physical interest in molecular physics, the present quantization rule not only yields a good approximation to the exact solution of the Schrodinger equation, but yields more precise energies than those obtained with the usual BS and/or WKB quantization rules. Among the examples considered numerically are the Poeschl-Teller potential and several anharmonic oscillator potentials. which simulate molecular vibrational spectra and the problem of an isolated quantum well structure subject to an external electric field.

Quantum toy model for black-hole backreaction

We propose a simple quantum field theoretical toy model for black-hole evaporation and study the backreaction of Hawking radiation onto the classical background. It turns out that the horizon is also pushed back in this situation (i.e., the interior region shrinks) though this backreaction is not caused by energy conservation but by momentum balance. The effective heat capacity and induced entropy variation can have both signs-depending on the parameters of the model.