Light emission and current rectification in a molecular device: Experiment and theory

We have investigated optical and transport properties of the molecular structure 2,3,4,5-tetraphenyl-1-phenylethynyl-cyclopenta-2,4-dienol experimentally and theoretically. The optical spectrum was calculated using Hartree-Fock-intermediate neglect of differential overlap-configuration interaction model. The experimental photoluminescence spectrum showed a peak around 470nm which was very well described by the modeling. Electronic transport measurements showed a diode-like effect with a strong current rectification. A phenomenological microscopic model based on non-equilibrium Green's function technique was proposed and a very good description electronic transport was obtained. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4767457]

The search for a potentially new molecular species, SiAs: A theoretical contribution

Electronic states of a new molecular species, SiAs, correlating with the three lowest dissociation channels are characterized at a high-level of theory using the CASSCF/MRCI approach along with quintuple-xi quality basis sets. This characterization includes potential energy curves, vibrational energy levels, spectroscopic parameters, dipole and transition dipole moment functions, transition probabilities, and radiative lifetimes. For the ground state (X-2 Pi), an assessment of spin-orbit effects and the interaction with the close-lying A(2)Sigma(+) state is also reported. Similarities and differences with other isovalent species such as SiP and CAs are also discussed.

A theoretical contribution characterizing a potentially new molecular species: MgAs

A new molecular species, MgAs, is investigated theoretically for the first time at the CASSCF/MRCI level using quintuple-zeta quality basis sets. Potential energy curves for the lowest-lying electronic states are presented as well as the associated spectroscopic constants. Dipole and transition moment functions for selected states complement this characterization. Estimates of transition probabilities and radiative life-times for the most important transitions are also reported. The effect of spin-orbit interactions is clearly reflected on the potential energy curves. Comparisons with BeAs, BeN, and BeP are made where pertinent. (C) 2011 Elsevier B.V. All rights reserved.

Theoretical study of the absorption and nonradiative deactivation of 1-nitronaphthalene in the low-lying singlet and triplet excited states including methanol and ethanol solvent effects

The photophysics of the 1-nitronaphthalene molecular system, after the absorption transition to the first singlet excited state, is theoretically studied for investigating the ultrafast multiplicity change to the triplet manifold. The consecutive transient absorption spectra experimentally observed in this molecular system are also studied. To identify the electronic states involved in the nonradiative decay, the minimum energy path of the first singlet excited state is obtained using the complete active space self-consistent field//configurational second-order perturbation approach. A near degeneracy region was found between the first singlet and the second triplet excited states with large spin-orbit coupling between them. The intersystem crossing rate was also evaluated. To support the proposed deactivation model the transient absorption spectra observed in the experiments were also considered. For this, computer simulations using sequential quantum mechanic-molecular mechanic methodology was used to consider the solvent effect in the ground and excited states for proper comparison with the experimental results. The absorption transitions from the second triplet excited state in the relaxed geometry permit to describe the transient absorption band experimentally observed around 200 fs after the absorption transition. This indicates that the T-2 electronic state is populated through the intersystem crossing presented here. The two transient absorption bands experimentally observed between 2 and 45 ps after the absorption transition are described here as the T-1 -> T-3 and T-1 -> T-5 transitions, supporting that the intermediate triplet state (T-2) decays by internal conversion to T-1. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4738757]

The radical SeCl: A theoretical contribution to the characterization of its low-lying electronic states

All doublet and quartet electronic states correlating with the first dissociation channel of SeCl and some Rydberg states are investigated theoretically at the CASSCF/MRCI level of theory using extended basis sets, including the contribution of spin-orbit effects. The similarity of the potential energy curves with those of SeF suggests that spectroscopic constants for the ground (X (2)Pi) and the first excited quartet (a(4)Sigma) of SeCl could also be determined via an emission resulting from the reaction of selenium with atomic chlorine. The coupling constant of the ground state at R-e is estimated as -1610 cm (1). The potential energy curves calculated and the derived spectroscopic constants do not support the interpretation and assignment of the scarce transitions recorded experimentally as due to (2)Pi-(2)Pi emissions. That the few observed lines might arise from transitions from the state b(4)Sigma(-)(1/2) to a very high vibrational level of the state a(4)Sigma(-)(1/2) is an open possibility, however, the number of vibrational states and the calculated Delta G(1/2) differ significantly from the reported ones. (C) 2012 Elsevier B. V. All rights reserved.

A theoretical study of SnF2+, SnCl2+, and SnO2+ and their experimental search

We present a detailed theoretical study of the stability of the gas-phase diatomic dications SnF2+, SnCl2+, and SnO2+ using ab initio computer calculations. The ground states of SnF2+, SnCl2+, and SnO2+ are thermodynamically stable, respectively, with dissociation energies of 0.45, 0.30, and 0.42 eV. Whereas SnF2+ dissociates into Sn2+ + F, the long range behaviour of the potential energy curves of SnCl2+ and SnO2+ is repulsive and wide barrier heights due to avoided crossing act as a kind of effective dissociation energy. Their equilibrium internuclear distances are 4.855, 5.201, and 4.852 a(0), respectively. The double ionisation energies (T-e) to form SnF2+, SnCl2+, and SnO2+ from their respective neutral parents are 25.87, 23.71, and 25.97 eV. We combine our theoretical work with the experimental results of a search for these doubly positively charged diatomic molecules in the gas phase. SnO2+ and SnF2+ have been observed for prolonged oxygen (O-16(-)) ion beam sputtering of a tin metal foil and of tin (II) fluoride (SnF2) powder, respectively, for ion flight times of about 10(-5) s through a magnetic-sector mass spectrometer. In addition, SnCl2+ has been detected for O-16(-) ion surface bombardment of stannous (tin (II)) chloride (SnCl2) powder. To our knowledge, SnF2+ is a novel gas-phase molecule, whereas SnCl2+ had been detected previously by electron-impact ionization mass spectrometry, and SnO2+ had been observed before by spark source mass spectrometry as well as by atom probe mass spectrometry. We are not aware of any previous theoretical studies of these molecular systems. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4758475]

Intermolecular Clamping by Hydrogen Bonds: 2-Pyridone center dot NH3

A combined spectroscopic and ab initio theoretical study of the doubly hydrogen-bonded complex of 2-pyridone (2PY) with NH3 has been performed. The S-1 <- S-0 spectrum extends up to approximate to 1200 cm(-1) above the 0(0)(0) band, close to twice the range observed for 2PY. The S-1 state nonradiative decay for vibrations above approximate to 300 cm(-1) in the NH3 complex is dramatically slowed down relative to bare 2PY. Also, the Delta v=2,4,... overtone bands of the v(1)' and v(2)' out-of-plane vibrations that dominate the low-energy spectral region of 2PY are much weaker or missing for 2PY center dot NH3, which implies that the bridging (2PY)NH center dot center dot center dot NH3 and H2NH center dot center dot center dot O=C H-bonds clamp the 2PY at a planar geometry in the S-1 state. The mass-resolved UV vibronic spectra of jet-cooled 2PY center dot NH3 and its H/D mixed isotopomers are measured using two-color resonant two-photon ionization spectroscopy. The S-0 and S-1 equilibrium structures and normal-mode frequencies are calculated by density functional (B3LYP) and correlated ab initio methods (MP2 and approximate second-order coupled-cluster, CC2). The S-1 <- S-0 vibronic assignments are based on configuration interaction singles (CIS) and CC2 calculations. A doubly H-bonded bridged structure of C-S symmetry is predicted, in agreement with that of Held and Pratt [J. Am. Chem. Soc. 1993, 115, 9718]. While the B3LYP and MP2 calculated rotational constants are in very good agreement with experiment, the calculated H2NH center dot center dot center dot O=C H-bond distance is approximate to 0.7 angstrom shorter than that derived by Held and Pratt. On the other hand, this underlines their observation that ammonia can act as a strong H-bond donor when built into an H-bonded bridge. The CC2 calculations predict the H2NH center dot center dot center dot O distance to increase by 0.2 angstrom upon S-1 <- S-0 electronic excitation, while the (2PY)NH center dot center dot center dot NH3 H-bond remains nearly unchanged. Thus, the expansion of the doubly H-bonded bridge in the excited state is asymmetric and almost wholly due to the weakening of the interaction of ammonia with the keto acceptor group.

Zone design of specific sizes using adaptive additively weighted voronoi diagrams

Territory or zone design processes entail partitioning a geographic space, organized as a set of areal units, into different regions or zones according to a specific set of criteria that are dependent on the application context. In most cases, the aim is to create zones of approximately equal sizes (zones with equal numbers of inhabitants, same average sales, etc.). However, some of the new applications that have emerged, particularly in the context of sustainable development policies, are aimed at defining zones of a predetermined, though not necessarily similar, size. In addition, the zones should be built around a given set of seeds. This type of partitioning has not been sufficiently researched; therefore, there are no known approaches for automated zone delimitation. This study proposes a new method based on a discrete version of the adaptive additively weighted Voronoi diagram that makes it possible to partition a two-dimensional space into zones of specific sizes, taking both the position and the weight of each seed into account. The method consists of repeatedly solving a traditional additively weighted Voronoi diagram, so that each seed?s weight is updated at every iteration. The zones are geographically connected using a metric based on the shortest path. Tests conducted on the extensive farming system of three municipalities in Castile-La Mancha (Spain) have established that the proposed heuristic procedure is valid for solving this type of partitioning problem. Nevertheless, these tests confirmed that the given seed position determines the spatial configuration the method must solve and this may have a great impact on the resulting partition.

A parametric, experimental analysis of conical vortices on curved roofs of low-rise buildings

Different methods to reduce the high suction caused by conical vortices have been reported in the literature: vertical parapets, either solid or porous, placed at the roof edges being the most analysed configuration. Another method for alleviating the high suction peaks due to conical vortices is the use of some non-standard parapet configuration like cantilever parapets. In this paper the influence of roof curvature on the conical vortex pattern appearing on a curved roof (Fig. 1) when subject to oblique winds is experimentally analysed by testing the mean pressure distribution on the curved roofs of low-rise building models in a wind tunnel. Also, the efficiency of cantilever parapets to reduce mean suction loads on curved roofs is experimentally checked. Very high suction loads have been measured on curved roofs, the magnitude of these high suction loads being significantly decreased when cantilever parapets are used. Thus, the suitability of these parapets to reduce wind pressure loads on curved roofs is demonstrated.

Wind tunnel analysis on the influence of cantilever parapets on the wind loads on curved roofs

Different methods to reduce the high suction caused by conical vortices have been reported in the literature: vertical parapets, either solids or porous, placed at the roof edges being the most analysed configuration. Another method for alleviating the high suction peaks due to conical vortices is to round the roof edges. Very recently, the use of some non-standard parapet configurations, like cantilever parapets, has been suggested. In this paper, its efficiency to reduce suction loads on curved roofs is experimentally checked by testing the pressure distribution on the curved roof of a low-rise building model in a wind tunnel. Very high suction loads have been measured on this model, the magnitude of these high suction loads being significantly decreased when cantilever...

Dynamic interactions between solids and viscous liquids with free surface = Interacciones dinámicas entre sólidos y líquidos viscosos con superficie libre

En esta tesis se investiga la interacción entre un fluido viscoso y un cuerpo sólido en presencia de una superficie libre. El problema se expresa teóricamente poniendo especial atención a los aspectos de conservación de energía y de la interacción del fluido con el cuerpo. El problema se considera 2D y monofásico, y un desarrollo matemático permite una descomposición de los términos disipativos en términos relacionados con la superficie libre y términos relacionados con la enstrofía. El modelo numérico utilizado en la tesis se basa en el método sin malla Smoothed Particle Hydrodynamics (SPH). De manera análoga a lo que se hace a nivel continuo, las propiedades de conservación se estudian en la tesis con el sistema discreto de partículas. Se tratan también las condiciones de contorno de un cuerpo que se mueve en un flujo viscoso, implementadas con el método ghost-fluid. Se ha desarrollado un algoritmo explícito de interacción fluido / cuerpo. Se han documentado algunos casos de modo detallado con el objetivo de comprobar la capacidad del modelo para reproducir correctamente la disipación de energía y el movimiento del cuerpo. En particular se ha investigado la atenuación de una onda estacionaria, comparando la simulación numérica con predicciones teóricas. Se han realizado otras pruebas para monitorizar la disipación de energía para flujos más violentos que implican la fragmentación de la superficie libre. La cantidad de energía disipada con los diferentes términos se ha evaluado en los casos estudiados con el modelo numérico. Se han realizado otras pruebas numéricas para verificar la técnica de modelización de la interacción fluido / cuerpo, concretamente las fuerzas ejercidas por las olas en cuerpos con formas simples, y el equilibrio de un cuerpo flotante con una forma compleja. Una vez que el modelo numérico ha sido validado, se han realizado simulaciones numéricas para obtener una comprensión más completa de la física implicada en casos (casi) realistas sobre los había aspectos que no se conocían suficientemente. En primer lugar se ha estudiado el el flujo alrededor de un cilindro bajo la superficie libre. El estudio se ha realizado con un número de Reynolds moderado, para un rango de inmersiones del cilindro y números de Froude. La solución numérica permite una investigación de los patrones complejos que se producen. La estela del cilindro interactúa con la superficie libre. Se han identificado algunos inestabilidades características. El segundo estudio se ha realizado sobre el problema de sloshing, tanto experimentalmente como numéricamente. El análisis se restringe a aguas poco profundas y con oscilación horizontal, pero se ha estudiado un gran número de condiciones, lo que lleva a una comprensión bastante completa de los sistemas de onda involucradas. La última parte de la tesis trata también sobre un problema de sloshing pero esta vez el tanque está oscilando con rotación y hay acoplamiento con un sistema mecánico. El sistema se llama pendulum-TLD (Tuned Liquid Damper - con líquido amortiguador). Este tipo de sistema se utiliza normalmente para la amortiguación de las estructuras civiles. El análisis se ha realizado analíticamente, numéricamente y experimentalmente utilizando líquidos con viscosidades diferentes, centrándose en características no lineales y mecanismos de disipación. ABSTRA C T The subject of the present thesis is the interaction between a viscous fluid and a solid body in the presence of a free surface. The problem is expressed first theoretically with a particular focus on the energy conservation and the fluid-body interaction. The problem is considered 2D and monophasic, and some mathematical development allows for a decomposition of the energy dissipation into terms related to the Free Surface and others related to the enstrophy. The numerical model used on the thesis is based on Smoothed Particle Hydrodynamics (SPH): a computational method that works by dividing the fluid into particles. Analogously to what is done at continuum level, the conservation properties are studied on the discrete system of particles. Additionally the boundary conditions for a moving body in a viscous flow are treated and discussed using the ghost-fluid method. An explicit algorithm for handling fluid-body coupling is also developed. Following these theoretical developments on the numerical model, some test cases are devised in order to test the ability of the model to correctly reproduce the energy dissipation and the motion of the body. The attenuation of a standing wave is used to compare what is numerically simulated to what is theoretically predicted. Further tests are done in order to monitor the energy dissipation in case of more violent flows involving the fragmentation of the free-surface. The amount of energy dissipated with the different terms is assessed with the numerical model. Other numerical tests are performed in order to test the fluid/body interaction method: forces exerted by waves on simple shapes, and equilibrium of a floating body with a complex shape. Once the numerical model has been validated, numerical tests are performed in order to get a more complete understanding of the physics involved in (almost) realistic cases. First a study is performed on the flow passing a cylinder under the free surface. The study is performed at moderate Reynolds numbers, for various cylinder submergences, and various Froude numbers. The capacity of the numerical solver allows for an investigation of the complex patterns which occur. The wake from the cylinder interacts with the free surface, and some characteristical flow mechanisms are identified. The second study is done on the sloshing problem, both experimentally and numerically. The analysis is restrained to shallow water and horizontal excitation, but a large number of conditions are studied, leading to quite a complete understanding of the wave systems involved. The last part of the thesis still involves a sloshing problem but this time the tank is rolling and there is coupling with a mechanical system. The system is named pendulum-TLD (Tuned Liquid Damper). This kind of system is normally used for damping of civil structures. The analysis is then performed analytically, numerically and experimentally for using liquids with different viscosities, focusing on non-linear features and dissipation mechanisms.

Photodissociation of benzene under collision-free conditions: An ab initio/Rice-Ramsperger-Kassel-Marcus study

The ab initio/Rice-Ramsperger-Kassel-Marcus (RRKM) approach has been applied to investigate the photodissociation mechanism of benzene at various wavelengths upon absorption of one or two UV photons followed by internal conversion into the ground electronic state. Reaction pathways leading to various decomposition products have been mapped out at the G2M level and then the RRKM and microcanonical variational transition state theories have been applied to compute rate constants for individual reaction steps. Relative product yields (branching ratios) for C6H5+H, C6H4+H-2, C4H4+C2H2, C4H2+C2H4, C3H3+C3H3, C5H3+CH3, and C4H3+C2H3 have been calculated subsequently using both numerical integration of kinetic master equations and the steady-state approach. The results show that upon absorption of a 248 nm photon dissociation is too slow to be observable in molecular beam experiments. In photodissociation at 193 nm, the dominant dissociation channel is H atom elimination (99.6%) and the minor reaction channel is H-2 elimination, with the branching ratio of only 0.4%. The calculated lifetime of benzene at 193 nm is about 11 mus, in excellent agreement with the experimental value of 10 mus. At 157 nm, the H loss remains the dominant channel but its branching ratio decreases to 97.5%, while that for H-2 elimination increases to 2.1%. The other channels leading to C3H3+C3H3, C5H3+CH3, C4H4+C2H2, and C4H3+C2H3 play insignificant role but might be observed. For photodissociation upon absorption of two UV photons occurring through the neutral hot benzene mechanism excluding dissociative ionization, we predict that the C6H5+H channel should be less dominant, while the contribution of C6H4+H-2 and the C3H3+C3H3, CH3+C5H3, and C4H3+C2H3 radical channels should significantly increase. (C) 2004 American Institute of Physics.

Studies of the shellside performance of shell-and-tube heat exchangers

Accurate prediction of shellside pressure drop in a baffled shell-and-tube heat exchanger is very difficult because of the complicated shellside geometry. Ideally, all the shellside fluid should be alternately deflected across the tube bundle as it traverses from inlet to outlet. In practice, up to 60% of the shellside fluid may bypass the tube bundle or leak through the baffles. This short-circuiting of the main flow reduces the efficiency of the exchanger. Of the various shellside methods, it is shown that only the multi-stream methods, which attempt to obtain the shellside flow distribution, predict the pressure drop with any degree of accuracy, the various predictions ranging from -30% to +70%, generally overpredicting. It is shown that the inaccuracies are mainly due to the manner in which baffle leakage is modelled. The present multi-stream methods do not allow for interactions of the various flowstreams, and yet it is shown that three main effects are identified, a) there is a strong interaction between the main cross flow and the baffle leakage streams, enhancing the crossflow pressure drop, b) there is a further short-circuit not considered previously i.e. leakage in the window, and c) the crossflow does not penetrate as far, on average, as previously supposed. Models are developed for each of these three effects, along with a new windowflow pressure drop model, and it is shown that the effect of baffle leakage in the window is the most significant. These models developed to allow for various interactions, lead to an improved multi-stream method, named the "STREAM-INTERACTION" method. The overall method is shown to be consistently more accurate than previous methods, with virtually all the available shellside data being predicted to within ±30% and over 60% being within ±20%. The method is, thus, strongly recommended for use as a design method.

Energy levels and radiative rates for Cr-like Cu VI and Zn VII

Energy levels and radiative rates (. A-values) for transitions in Cr-like Cu VI and Zn VII are reported. These data are determined in the quasi-relativistic approach (QR), by employing a very large configuration interaction (CI) expansion which is highly important for these ions. No radiative rates are available in the literature to compare with our results, but our calculated energies are in close agreement with those compiled by NIST and other available theoretical data, for a majority of the levels. The A-values (and resultant lifetimes) are listed for all significantly contributing E1, E2 and M1 radiative transitions among the energetically lowest 322 levels of each ion.

Radiative rates for E1, E2, M1, and M2 transitions in S-like to F-like tungsten ions (W LIX to W LXVI)

Calculations of energy levels, radiative rates and lifetimes are reported for eight ions of tungsten, i.e. S-like (W LIX) to F-like (W LXVI). A large number of levels have been considered for each ion and extensive configuration interaction has been included among a range of configurations. For the calculations, the general-purpose relativistic atomic structure package (. grasp) has been adopted, and radiative rates (as well as oscillator strengths and line strengths) are listed for all E1, E2, M1, and M2 transitions of the ions. Comparisons have been made with earlier available experimental and theoretical energies, although these are limited to only a few levels for most ions. Therefore for additional accuracy assessments, particularly for energy levels, analogous calculations have been performed with the flexible atomic code (. fac).