Nonlinear spectrum effect on the coherent control of molecular systems

This work demonstrates that the detuning of the fs-laser spectrum from the two-photon absorption band of organic materials can be used to reach further control of the two-photon absorption by pulse spectral phase manipulation. We investigate the coherent control of the two-photon absorption in imidazole-thiophene core compounds presenting distinct two-photon absorption spectra. The coherent control, performed using pulse phase shaping and genetic algorithm, exhibited different growth rates for each sample. Such distinct trends were explained by calculating the two-photon absorption probability considering the intrapulse interference mechanism, taking into account the two-photon absorption spectrum of the samples. Our results indicate that tuning the relative position between the nonlinear absorption and the pulse spectrum can be used as a novel strategy to optimize the two-photon absorption in broadband molecular systems. (C) 2011 Elsevier B.V. All rights reserved.

Influence of super-ohmic dissipation on a disordered quantum critical point

We investigate the combined influence of quenched randomness and dissipation on a quantum critical point with O(N) order-parameter symmetry. Utilizing a strong-disorder renormalization group, we determine the critical behavior in one space dimension exactly. For super-ohmic dissipation, we find a Kosterlitz-Thouless type transition with conventional (power-law) dynamical scaling. The dynamical critical exponent depends on the spectral density of the dissipative baths. We also discuss the Griffiths singularities, and we determine observables.

Tightened Lieb-Oxford Bound for Systems of Fixed Particle Number

The Lieb-Oxford bound is a constraint upon approximate exchange-correlation functionals. We explore a nonempirical tightening of that bound in both universal and electron number-dependent form. The test functional is PBE. Regarding both atomization energies (slightly worsened) and bond lengths (slightly improved), we find the PBE functional to be remarkably insensitive to the value of the Lieb-Oxford bound. This both rationalizes the use of the original Lieb-Oxford constant in PBE and suggests that enhancement factors more sensitive to sharpened constraints await discovery.

Orbital-polarization terms: From a phenomenological to a first-principles description of orbital magnetism in density-functional theory

Phenomenological orbital-polarizition (OP) terms have been repeatedly introduced in the single-particle equations of spin-density-functional theory, in order to improve the description of orbital magnetic moments in systems containing transition metal ions. Here we show that these ad hoc corrections can be interpreted as approximations to the exchange-correlation vector potential A(xc) of current-density functional theory (CDFT). This connection provides additional information on both approaches: phenomenological OP terms are connected to first-principles theory, leading to a rationale for their empirical success and a reassessment of their limitations and the approximations made in their derivation. Conversely, the connection of OP terms with CDFT leads to a set of simple approximations to the CDFT potential A(xc), with a number of desirable features that are absent from electron-gas-based functionals. (C) 2008 Wiley Periodicals, Inc.

A study of the relaxation dynamics in a quadrupolar NMR system using Quantum State Tomography

This article reports a relaxation study in an oriented system containing spin 3/2 nuclei using quantum state tomography (QST). The use of QST allowed evaluating the time evolution of all density matrix elements starting from several initial states. Using an appropriated treatment based on the Redfield theory, the relaxation rate of each density matrix element was measured and the reduced spectral densities that describe the system relaxation were determined. All the experimental data could be well described assuming pure quadrupolar relaxation and reduced spectral densities corresponding to a superposition of slow and fast motions. The data were also analyzed in the context of Quantum Information Processing, where the coherence loss of each qubit of the system was determined using the partial trace operation. (C) 2008 Elsevier Inc. All rights reserved.

The intramolecular charge transfer in a donor-pi-acceptor dianion probed by resonance Raman spectroscopy and quantum chemical calculations

The dideprotonation of 4-(4-nitrophenylazo)resorcinol generates an anionic species with substantial electronic pi delocalization. As compared to the parent neutral species, the anionic first excited electronic transition, characterized as an intramolecular charge transfer (ICT) from the CO(-) groups to the NO(2) moiety, shows a drastic red shift of ca. 200 nm in the lambda(max) in the UV-vis spectrum, leading to one of the lowest ICT energies observed (lambda(max) = 630 nm in dimethyl sulfoxide (DMSO)) in this class of push-pull molecular systems. Concomitantly, a threefold increase in the molar absorptivity (epsilon(max)) in comparison to the neutral species is observed. The resonance Raman enhancement profiles reveal that in the neutral species the chromophore involves several modes, as nu(C-N), nu(N=N), nu(C=C) and nu(s)(NO(2)), whereas in the dianion, there is a selective enhancement of the NO(2) vibrational modes. The quantum chemical calculations of the electronic transitions and vibrational wavenumbers led to a consistent analysis of the enhancement patterns observed in the resonance Raman spectra. Copyright (C) 2009 John Wiley & Sons, Ltd.

Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

The electronic delocalization in para-substituted beta-nitrostyrenes probed by resonance Raman spectroscopy and quantum-chemical calculations

The electronic (UV-vis) and resonance Raman (RR) spectra of a series of para-substituted trans-beta-nitrostyrenes were investigated to determine the influence of the electron donating properties of the substituent (X = H, NO2, COOH, Cl, OCH3, OH, N(CH3)(2), and O-) on the extent of the charge transfer to the electron-withdrawing NO2 group directly linked to the ethylenic (C=C) unit. The Raman spectra and quantum chemical calculations show clearly the correlation of the electron donating power of the X group with the wavenumbers of the nu(s)(NO2) and nu (C=C)(sty) normal modes. In conditions of resonance with the lowest excited electronic state, one observes for X = OH and N(CH3)2 that the symmetric stretching of the NO2. nu(s)(NO2), is the most substantially enhanced mode, whereas for X = O-, the chromophore is extended over the whole molecule, with substantial enhancement of several carbon backbone modes. Copyright (c) 2008 John Wiley & Sons, Ltd.

Investigating the Nature of Noble Gas-Copper Bonds by the Quantum Theory of Atoms in Molecules

We investigated noble gas copper bonds in linear complexes represented by the NgCuX general formula in which Ng and X stand for a noble gas (neon, argon, krypton, or xenon) and a halogen (fluorine, chlorine or bromine), respectively, by coupled cluster methods and modified cc-pVQZ basis sets. The quantum theory of atoms in molecules (QTAIM) shows a linear relation between the dissociation energy or noble gas-copper bonds and the amount of electronic charge transferred mainly from the noble gas to copper during complexation. Large changes in the QTAIM quadrupole moments of copper and noble gases resulting from this bonding and a comparison between NgCuX and NgNaCl systems indicate that these noble gas-copper bonds should be better interpreted as predominantly covalent. Finally, QTAIM atomic dipoles of noble gases in NgNaCl systems agree satisfactorily with atomic dipoles given by a simple model for these NgNa van der Waals bonds.

Heat losses and thermal performance of commercial combined solar and pellet heating systems

Various pellet heating systems are marketed in Sweden, some of them in combination with a solar heating system. Several types of pellet heating units are available and can be used for a combined system. This article compares four typical combined solar and pellet heating systems: System 1 and 2 two with a pellet stove, system 3 with a store integrated pellet burner and system 4 with a pellet boiler. The lower efficiency of pellet heaters compared to oil or gas heaters increases the primary energy demand. Consequently heat losses of the various systems have been studied. The systems have been modeled in TRNSYS and simulated with parameters identified from measurements. For almost all systems the flue gas losses are the main heat losses except for system 3 where store heat losses prevail. Relevant are also the heat losses of the burner and the boiler to the ambient. Significant leakage losses are noticed for system 3 and 4. For buildings with an open internal design system 1 is the most efficient solution. Other buildings should preferably apply system 3. The right choice of the system depends also on whether the heater is placed inside or outside of the heated are. A large potential for system optimization exist for all studied systems, which when applied could alter the relative merits of the different system types.

Combined solar and pellet heating systems for single-family houses : How to achieve decreased electricity usage, increased system efficiency and increased solar gains

In Sweden, there are about 0.5 million single-family houses that are heated by electricity alone, and rising electricity costs force the conversion to other heating sources such as heat pumps and wood pellet heating systems. Pellet heating systems for single-family houses are currently a strongly growing market. Future lack of wood fuels is possible even in Sweden, and combining wood pellet heating with solar heating will help to save the bio-fuel resources. The objectives of this thesis are to investigate how the electrically heated single-family houses can be converted to pellet and solar heating systems, and how the annual efficiency and solar gains can be increased in such systems. The possible reduction of CO-emissions by combining pellet heating with solar heating has also been investigated. Systems with pellet stoves (both with and without a water jacket), pellet boilers and solar heating have been simulated. Different system concepts have been compared in order to investigate the most promising solutions. Modifications in system design and control strategies have been carried out in order to increase the system efficiency and the solar gains. Possibilities for increasing the solar gains have been limited to investigation of DHW-units for hot water production and the use of hot water for heating of dishwashers and washing machines via a heat exchanger instead of electricity (heat-fed appliances). Computer models of pellet stoves, boilers, DHW-units and heat-fed appliances have been developed and the parameters for the models have been identified from measurements on real components. The conformity between the models and the measurements has been checked. The systems with wood pellet stoves have been simulated in three different multi-zone buildings, simulated in detail with heat distribution through door openings between the zones. For the other simulations, either a single-zone house model or a load file has been used. Simulations were carried out for Stockholm, Sweden, but for the simulations with heat-fed machines also for Miami, USA. The foremost result of this thesis is the increased understanding of the dynamic operation of combined pellet and solar heating systems for single-family houses. The results show that electricity savings and annual system efficiency is strongly affected by the system design and the control strategy. Large reductions in pellet consumption are possible by combining pellet boilers with solar heating (a reduction larger than the solar gains if the system is properly designed). In addition, large reductions in carbon monoxide emissions are possible. To achieve these reductions it is required that the hot water production and the connection of the radiator circuit is moved to a well insulated, solar heated buffer store so that the boiler can be turned off during the periods when the solar collectors cover the heating demand. The amount of electricity replaced using systems with pellet stoves is very dependant on the house plan, the system design, if internal doors are open or closed and the comfort requirements. Proper system design and control strategies are crucial to obtain high electricity savings and high comfort with pellet stove systems. The investigated technologies for increasing the solar gains (DHW-units and heat-fed appliances) significantly increase the solar gains, but for the heat-fed appliances the market introduction is difficult due to the limited financial savings and the need for a new heat distribution system. The applications closest to market introduction could be for communal laundries and for use in sunny climates where the dominating part of the heat can be covered by solar heating. The DHW-unit is economical but competes with the internal finned-tube heat exchanger which is the totally dominating technology for hot water preparation in solar combisystems for single-family houses.

Quantum control of electromagnetically induced transparency dispersion via atomic tunneling in a double-well Bose-Einstein condensate

Electromagnetically induced transparency (EIT) is an important tool for controlling light propagation and nonlinear wave mixing in atomic gases with potential applications ranging from quantum computing to table top tests of general relativity. Here we consider EIT in an atomic Bose-Einstein condensate (BEC) trapped in a double-well potential. A weak probe laser propagates through one of the wells and interacts with atoms in a three-level Lambda configuration. The well through which the probe propagates is dressed by a strong control laser with Rabi frequency Omega(mu), as in standard EIT systems. Tunneling between the wells at the frequency g provides a coherent coupling between identical electronic states in the two wells, which leads to the formation of interwell dressed states. The macroscopic interwell coherence of the BEC wave function results in the formation of two ultranarrow absorption resonances for the probe field that are inside of the ordinary EIT transparency window. We show that these new resonances can be interpreted in terms of the interwell dressed states and the formation of a type of dark state involving the control laser and the interwell tunneling. To either side of these ultranarrow resonances there is normal dispersion with very large slope controlled by g. We discuss prospects for observing these ultranarrow resonances and the corresponding regions of high dispersion experimentally.

Designing Agent-Oriented Systems by Analysing Agent Interactions

We propose a preliminary methodology for agent-oriented software engineering based on the idea of agent interaction analysis. This approach uses interactions between undetermined agents as the primary component of analysis and design. Agents as a basis for software engineering are useful because they provide a powerful and intuitive abstraction which can increase the comprehensiblity of a complex design. The paper describes a process by which the designer can derive the interactions that can occur in a system satisfying the given requirements and use them to design the structure of an agent-based system, including the identification of the agents themselves. We suggest that this approach has the flexibility necessary to provide agent-oriented designs for open and complex applications, and has value for future maintenance and extension of these systems.

Towards a Monitoring Framework for Agent-Based Contract Systems

The behaviours of autonomous agents may deviate from those deemed to be for the good of the societal systems of which they are a part. Norms have therefore been proposed as a means to regulate agent behaviours in open and dynamic systems, and may be encoded in electronic contracts in order to specify the obliged, permitted and prohibited behaviours of agents that are signatories to such contracts. Enactment and management of electronic contracts thus enables the use of regulatory mechanisms to ensure that agent behaviours comply with the encoded norms. To facilitate such mechanisms requires monitoring in order to detect and explain violation of norms. In this paper we propose a framework for monitoring that is to be implemented and integrated into a suite of contract enactment and management tools. The framework adopts a non-intrusive approach to monitoring, whereby the states of a contract with respect to its contained norms can be inferred on the basis of messages exchanged. Specifically, the framework deploys agents that observe messages sent between contract signatories, where these messages correspond to agent behaviours and therefore indicate whether norms are, or are in danger of, being violated.

A Framework for Monitoring Agent-Based Normative Systems

The behaviours of autonomous agents may deviate from those deemed to be for the good of the societal systems of which they are a part. Norms have therefore been proposed as a means to regulate agent behaviours in open and dynamic systems, where these norms specify the obliged, permitted and prohibited behaviours of agents. Regulation can effectively be achieved through use of enforcement mechanisms that result in a net loss of utility for an agent in cases where the agent's behaviour fails to comply with the norms. Recognition of compliance is thus crucial for achieving regulation. In this paper we propose a generic architecture for observation of agent behaviours, and recognition of these behaviours as constituting, or counting as, compliance or violation. The architecture deploys monitors that receive inputs from observers, and processes these inputs together with transition network representations of individual norms. In this way, monitors determine the fulfillment or violation status of norms. The paper also describes a proof of concept implementation and deployment of monitors in electronic contracting environments.