Generalized atoms in molecules approach (GAIM approach)

This thesis involves two parts. The first is a new-proposed theoretical approach called generalized atoms in molecules (GAIM). The second is a computational study on the deamination reaction of adenine with OH⁻/nH₂O (n=0, 1, 2, 3) and 3H₂O. The GAIM approach aims to solve the energy of each atom variationally in the first step and then to build the energy of a molecule from each atom. Thus the energy of a diatomic molecule (A-B) is formulated as a sum of its atomic energies, EA and EB. Each of these atomic energies is expressed as, EA = Hᴬ + Vₑₑᴬᴬ + 1/2Vₑₑᴬ<>ᴮ EB = Hᴮ + Vₑₑᴮᴮ + 1/2Vₑₑᴬ<>ᴮ where; Hᴬ and Hᴮ are the kinetic and nuclear attraction energy of electrons of atoms A and B, respectively; Vₑₑᴬᴬ and Vₑₑᴮᴮ are the interaction energy between the electrons on atoms A and B, respectively; and Vₑₑᴬ<>ᴮ is the interaction energy between the electrons of atom A with the electrons of atom B. The energy of the molecule is then minimized subject to the following constraint, |ρA(r)dr + |ρB(r)dr = N where ρA(r) and ρB(r) are the electron densities of atoms A and B, respectively, and N is the number of electrons. The initial testing of the performance of GAIM was done through calculating dissociation curves for H₂, LiH, Li₂, BH, HF, HCl, N₂, F₂, and Cl₂. The numerical results show that GAIM performs very well with H₂, LiH, Li₂, BH, HF, and HCl. GAIM shows convergence problems with N₂, F₂, and Cl₂ due to difficulties in reordering the degenerate atomic orbitals Pₓ, Py, and Pz in N, F, and Cl atoms. Further work for the development of GAIM is required. Deamination of adenine results in one of several forms of premutagenic lesions occurring in DNA. In this thesis, mechanisms for the deamination reaction of adenine with OH⁻/nH₂O, (n = 0, 1, 2, 3) and 3H₂O were investigated. HF/6-31G(d), B3LYP/6-31G(d), MP2/6-31G(d), and B3LYP/6-31+G(d) levels of theory were employed to optimize all the geometries. Energies were calculated at the G3MP2B3 and CBS-QB3 levels of theory. The effect of solvent (water) was computed using the polarizable continuum model (PCM). Intrinsic reaction coordinate (IRC) calculations were performed for all transition states. Five pathways were investigated for the deamination reaction of adenine with OH⁻/nH₂O and 3H₂O. The first four pathways (A-D) begin with by deprotonation at the amino group of adenine by OH⁻, while pathway E is initiated by tautomerization of adenine. For all pathways, the next two steps involve the formation of a tetrahedral intermediate followed by dissociation to yield products via a 1,3-hydrogen shift. Deamination with a single OH⁻ has a high activation barrier (190 kJ mol⁻¹ using G3MP2B3 level) for the rate-determining step. Addition of one water molecule reduces this barrier by 68 kJ mol⁻¹ calculated at G3MP2B3 level. Adding more water molecules decreases the overall activation energy of the reaction, but the effect becomes smaller with each additional water molecule. The most plausible mechanism is pathway E, the deamination reaction of adenine with 3H₂O, which has an overall G3MP2B3 activation energy of 139 and 137 kJ mol⁻¹ in the gas phase and PCM, respectively. This barrier is lower than that for the deamination with OH⁻/3H₂O by 6 and 2 kJ mol⁻¹ in the gas phase and PCM, respectively.

Strong shift equivalence, algebraic K-theory, and isolating zero-dimensional dynamics on manifolds

We study the relations of shift equivalence and strong shift equivalence for matrices over a ring $\mathcal{R}$, and establish a connection between these relations and algebraic K-theory. We utilize this connection to obtain results in two areas where the shift and strong shift equivalence relations play an important role: the study of finite group extensions of shifts of finite type, and the Generalized Spectral Conjectures of Boyle and Handelman for nonnegative matrices over subrings of the real numbers. We show the refinement of the shift equivalence class of a matrix $A$ over a ring $\mathcal{R}$ by strong shift equivalence classes over the ring is classified by a quotient $NK_{1}(\mathcal{R}) / E(A,\mathcal{R})$ of the algebraic K-group $NK_{1}(\calR)$. We use the K-theory of non-commutative localizations to show that in certain cases the subgroup $E(A,\mathcal{R})$ must vanish, including the case $A$ is invertible over $\mathcal{R}$. We use the K-theory connection to clarify the structure of algebraic invariants for finite group extensions of shifts of finite type. In particular, we give a strong negative answer to a question of Parry, who asked whether the dynamical zeta function determines up to finitely many topological conjugacy classes the extensions by $G$ of a fixed mixing shift of finite type. We apply the K-theory connection to prove the equivalence of a strong and weak form of the Generalized Spectral Conjecture of Boyle and Handelman for primitive matrices over subrings of $\mathbb{R}$. We construct explicit matrices whose class in the algebraic K-group $NK_{1}(\mathcal{R})$ is non-zero for certain rings $\mathcal{R}$ motivated by applications. We study the possible dynamics of the restriction of a homeomorphism of a compact manifold to an isolated zero-dimensional set. We prove that for $n \ge 3$ every compact zero-dimensional system can arise as an isolated invariant set for a homeomorphism of a compact $n$-manifold. In dimension two, we provide obstructions and examples.

Formalizing operator task analysis

Human operators are unique in their decision making capability, judgment and nondeterminism. Their sense of judgment, unpredictable decision procedures, susceptibility to environmental elements can cause them to erroneously execute a given task description to operate a computer system. Usually, a computer system is protected against some erroneous human behaviors by having necessary safeguard mechanisms in place. But some erroneous human operator behaviors can lead to severe or even fatal consequences especially in safety critical systems. A generalized methodology that can allow modeling and analyzing the interactions between computer systems and human operators where the operators are allowed to deviate from their prescribed behaviors will provide a formal understanding of the robustness of a computer system against possible aberrant behaviors by its human operators. We provide several methodology for assisting in modeling and analyzing human behaviors exhibited while operating computer systems. Every human operator is usually given a specific recommended set of guidelines for operating a system. We first present process algebraic methodology for modeling and verifying recommended human task execution behavior. We present how one can perform runtime monitoring of a computer system being operated by a human operator for checking violation of temporal safety properties. We consider the concept of a protection envelope giving a wider class of behaviors than those strictly prescribed by a human task that can be tolerated by a system. We then provide a framework for determining whether a computer system can maintain its guarantees if the human operators operate within their protection envelopes. This framework also helps to determine the robustness of the computer system under weakening of the protection envelopes. In this regard, we present a tool called Tutela that assists in implementing the framework. We then examine the ability of a system to remain safe under broad classes of variations of the prescribed human task. We develop a framework for addressing two issues. The first issue is: given a human task specification and a protection envelope, will the protection envelope properties still hold under standard erroneous executions of that task by the human operators? In other words how robust is the protection envelope? The second issue is: in the absence of a protection envelope, can we approximate a protection envelope encompassing those standard erroneous human behaviors that can be safely endured by the system? We present an extension of Tutela that implements this framework. The two frameworks mentioned above use Concurrent Game Structures (CGS) as models for both computer systems and their human operators. However, there are some shortcomings of this formalism for our uses. We add incomplete information concepts in CGSs to achieve better modularity for the players. We introduce nondeterminism in both the transition system and strategies of players and in the modeling of human operators and computer systems. Nondeterministic action strategies for players in \emph{i}ncomplete information \emph{N}ondeterministic CGS (iNCGS) is a more precise formalism for modeling human behaviors exhibited while operating a computer system. We show how we can reason about a human behavior satisfying a guarantee by providing a semantics of Alternating Time Temporal Logic based on iNCGS player strategies. In a nutshell this dissertation provides formal methodology for modeling and analyzing system robustness against both expected and erroneous human operator behaviors.

Dependence of the crossover exponent with the diffusion rate in the generalized contact process model

We study how the crossover exponent, phi, between the directed percolation (DP) and compact directed percolation (CDP) behaves as a function of the diffusion rate in a model that generalizes the contact process. Our conclusions are based in results pointed by perturbative series expansions and numerical simulations, and are consistent with a value phi = 2 for finite diffusion rates and phi = 1 in the limit of infinite diffusion rate.

Effects of naps at work on the sleepiness of 12-hour night shift nursing personnel

Background and objective: The purpose of the present study was to evaluate the effects of a nap at work on the sleepiness of 12-hour, night-shift (registered and assistant) nursing personnel.Methods: Twelve nurses filled out daily logs, the Karolinska Sleepiness Scale (KS), and wore wrist actigraphs for two periods of four continuous days.Results: Mean nap duration during the night shifts was 138.3 (SD+39.8) minutes. The mean sleepiness level assessed by the KS score was lower, 3.3 (SD±1.6), when the nap was taken during the first span (00:01 - 03:00h) of the night shift, compared with 6.6 (SD±1.0) when there was no nap. The mean sleepiness level assessed by the KS score was also lower, 3.6 (SD±0.9), when the nap was taken during the second span (03:01 - 06:00h) of the night shift, compared with 7.0 (SD±1.1) when there was no nap. Thus, napping either during the first or second part of the night shift reduces sleepiness of 12-hour, night-shift nursing personnel. Moreover, the mean duration of the first sleep episode after night work was longer in those who did not nap than in those who did. Conclusions: The results of this study show that napping during the 12-hour, night-shift results in less sleepiness at work and less need for recovery sleep after work

Diffractive phase-shift lithography photomask operating in proximity printing mode

A phase shift proximity printing lithographic mask is designed, manufactured and tested. Its design is based on a Fresnel computer-generated hologram, employing the scalar diffraction theory. The obtained amplitude and phase distributions were mapped into discrete levels. In addition, a coding scheme using sub-cells structure was employed in order to increase the number of discrete levels, thus increasing the degree of freedom in the resulting mask. The mask is fabricated on a fused silica substrate and an amorphous hydrogenated carbon (a:C-H) thin film which act as amplitude modulation agent. The lithographic image is projected onto a resist coated silicon wafer, placed at a distance of 50 mu m behind the mask. The results show a improvement of the achieved resolution - linewidth as good as 1.5 mu m - what is impossible to obtain with traditional binary masks in proximity printing mode. Such achieved dimensions can be used in the fabrication of MEMS and MOEMS devices. These results are obtained with a UV laser but also with a small arc lamp light source exploring the partial coherence of this source. (C) 2010 Optical Society of America

Data collapse, scaling functions, and analytical solutions of generalized growth models

We consider a nontrivial one-species population dynamics model with finite and infinite carrying capacities. Time-dependent intrinsic and extrinsic growth rates are considered in these models. Through the model per capita growth rate we obtain a heuristic general procedure to generate scaling functions to collapse data into a simple linear behavior even if an extrinsic growth rate is included. With this data collapse, all the models studied become independent from the parameters and initial condition. Analytical solutions are found when time-dependent coefficients are considered. These solutions allow us to perceive nontrivial transitions between species extinction and survival and to calculate the transition's critical exponents. Considering an extrinsic growth rate as a cancer treatment, we show that the relevant quantity depends not only on the intensity of the treatment, but also on when the cancerous cell growth is maximum.

A Paradigm Shift in Predoctoral Dental Curricula in Brazil: Evaluating the Process of Change

In 2002, the Brazilian Ministry of Education approved the official curricular guidelines for undergraduate courses in Brazil to be adopted by the nation's 188 dental schools. In 2005-06, the Brazilian Dental Education Association (BDEA) promoted workshops in forty-eight of the schools to verify the degree of transformation of the curriculum based on these guidelines. Among the areas analyzed were course philosophy (variables were v1: knowledge production based on the needs of the Brazilian Public Health System [BPHS]; v2: health determinants; and v3: postgraduate studies and permanent education); pedagogical skills (v4: curricular structure; v5: changes in pedagogic and didactic skills; and v6: course program orientation); and dental practice scenarios (v7: diversity of the scenarios for training/learning; v8: academic health care centers opened to the BPHS; and v9: participation of students in health care delivery for the population). The subjects consisted of faculty members (n=711), students (n=228), and employees (n=14). The results showed an incipient degree of curriculum transformation. The degree of innovation was statistically different depending on the type of university (public or private) for variables I, 2, 4, 5, 6, and 7. Private schools reported a higher level of innovation than public institutions. Resistance to transforming the dental curriculum according to the official guidelines may be linked to an ideological conception that supports the private practice model, continues to have faculty members direct all classroom activities, and prevents students from developing an understanding of professional practice as targeted towards the oral health needs of all segments of society.

Confronting dark energy models using galaxy cluster number counts

The mass function of cluster-size halos and their redshift distribution are computed for 12 distinct accelerating cosmological scenarios and confronted to the predictions of the conventional flat Lambda CDM model. The comparison with Lambda CDM is performed by a two-step process. First, we determine the free parameters of all models through a joint analysis involving the latest cosmological data, using supernovae type Ia, the cosmic microwave background shift parameter, and baryon acoustic oscillations. Apart from a braneworld inspired cosmology, it is found that the derived Hubble relation of the remaining models reproduces the Lambda CDM results approximately with the same degree of statistical confidence. Second, in order to attempt to distinguish the different dark energy models from the expectations of Lambda CDM, we analyze the predicted cluster-size halo redshift distribution on the basis of two future cluster surveys: (i) an X-ray survey based on the eROSITA satellite, and (ii) a Sunayev-Zeldovich survey based on the South Pole Telescope. As a result, we find that the predictions of 8 out of 12 dark energy models can be clearly distinguished from the Lambda CDM cosmology, while the predictions of 4 models are statistically equivalent to those of the Lambda CDM model, as far as the expected cluster mass function and redshift distribution are concerned. The present analysis suggests that such a technique appears to be very competitive to independent tests probing the late time evolution of the Universe and the associated dark energy effects.

ZETA DETERMINANT AND OPERATOR DETERMINANTS

We apply techniques of zeta functions and regularized products theory to study the zeta determinant of a class of abstract operators with compact resolvent, and in particular the relation with other spectral functions.

Generalized connectivity between any two nodes in a complex network

This article focuses on the identification of the number of paths with different lengths between pairs of nodes in complex networks and how these paths can be used for characterization of topological properties of theoretical and real-world complex networks. This analysis revealed that the number of paths can provide a better discrimination of network models than traditional network measurements. In addition, the analysis of real-world networks suggests that the long-range connectivity tends to be limited in these networks and may be strongly related to network growth and organization.

Study of the influence of indium segregation on the optical properties of InGaAs/GaAs quantum wells via split-operator method

In the case of quantum wells, the indium segregation leads to complex potential profiles that are hardly considered in the majority of the theoretical models. The authors demonstrated that the split-operator method is useful tool for obtaining the electronic properties in these cases. Particularly, they studied the influence of the indium surface segregation in optical properties of InGaAs/GaAs quantum wells. Photoluminescence measurements were carried out for a set of InGaAs/GaAs quantum wells and compared to the results obtained theoretically via split-operator method, showing a good agreement.

Generalized Sznajd model for opinion propagation

In the last decade the Sznajd model has been successfully employed in modeling some properties and scale features of both proportional and majority elections. We propose a version of the Sznajd model with a generalized bounded confidence rule-a rule that limits the convincing capability of agents and that is essential to allow coexistence of opinions in the stationary state. With an appropriate choice of parameters it can be reduced to previous models. We solved this model both in a mean-field approach (for an arbitrary number of opinions) and numerically in a Barabaacutesi-Albert network (for three and four opinions), studying the transient and the possible stationary states. We built the phase portrait for the special cases of three and four opinions, defining the attractors and their basins of attraction. Through this analysis, we were able to understand and explain discrepancies between mean-field and simulation results obtained in previous works for the usual Sznajd model with bounded confidence and three opinions. Both the dynamical system approach and our generalized bounded confidence rule are quite general and we think it can be useful to the understanding of other similar models.

Coexistence of interacting opinions in a generalized Sznajd model

The Sznajd model is a sociophysics model that mimics the propagation of opinions in a closed society, where the interactions favor groups of agreeing people. It is based in the Ising and Potts ferromagnetic models and, although the original model used only linear chains, it has since been adapted to general networks. This model has a very rich transient, which has been used to model several aspects of elections, but its stationary states are always consensus states. In order to model more complex behaviors, we have, in a recent work, introduced the idea of biases and prejudices to the Sznajd model by generalizing the bounded confidence rule, which is common to many continuous opinion models, to what we called confidence rules. In that work we have found that the mean field version of this model (corresponding to a complete network) allows for stationary states where noninteracting opinions survive, but never for the coexistence of interacting opinions. In the present work, we provide networks that allow for the coexistence of interacting opinions for certain confidence rules. Moreover, we show that the model does not become inactive; that is, the opinions keep changing, even in the stationary regime. This is an important result in the context of understanding how a rule that breeds local conformity is still able to sustain global diversity while avoiding a frozen stationary state. We also provide results that give some insights on how this behavior approaches the mean field behavior as the networks are changed.

Combined Monte Carlo and quantum mechanics study of the solvatochromism of phenol in water. The origin of the blue shift of the lowest pi-pi* transition

A combined and sequential use of Monte Carlo simulations and quantum mechanical calculations is made to analyze the spectral shift of the lowest pi-pi* transition of phenol in water. The solute polarization is included using electrostatic embedded calculations at the MP2/aug-cc-pVDZ level giving a dipole moment of 2.25 D, corresponding to an increase of 76% compared to the calculated gas-phase value. Using statistically uncorrelated configurations sampled from the MC simulation,first-principle size-extensive calculations are performed to obtain the solvatochromic shift. Analysis is then made of the origin of the blue shift. Results both at the optimized geometry and in room-temperature liquid water show that hydrogen bonds of water with phenol promote a red shift when phenol is the proton-donor and a blue shift when phenol is the proton-acceptor. In the case of the optimized clusters the calculated shifts are in very good agreement with results obtained from mass-selected free jet expansion experiments. In the liquid case the contribution of the solute-solvent hydrogen bonds partially cancels and the total shift obtained is dominated by the contribution of the outer solvent water molecules. Our best result, including both inner and outer water molecules, is 570 +/- 35 cm(-1), in very good agreement with the small experimental shift of 460 cm(-1) for the absorption maximum.