Experimental and Theoretical Study on the One- and Two-Photon Absorption Properties of Novel Organic Molecules Based on Phenylacetylene and Azoaromatic Moieties

This Article reports a combined experimental and theoretical analysis on the one and two-photon absorption properties of a novel class of organic molecules with a pi-conjugated backbone based on phenylacetylene (JCM874, FD43, and FD48) and azoaromatic (YB3p2S) moieties. Linear optical properties show that the phenylacetylene-based compounds exhibit strong molar absorptivity in the UV and high fluorescence quantum yield with lifetimes of approximately 2.0 ns, while the azoaromatic-compound has a strong absorption in the visible region with very low fluorescence quantum yield. The two-photon absorption was investigated employing nonlinear optical techniques and quantum chemical calculations based on the response functions formalism within the density functional theory framework. The experimental data revealed well-defined 2PA spectra with reasonable cross-section values in the visible and IR. Along the nonlinear spectra we observed two 2PA allowed bands, as well as the resonance enhancement effect due to the presence of one intermediate one-photon allowed state. Quantum chemical calculations revealed that the 2PA allowed bands correspond to transitions to states that are also one-photon allowed, indicating the relaxation of the electric-dipole selection rules. Moreover, using the theoretical results, we were able to interpret the experimental trends of the 2PA spectra. Finally, using a few-energy-level diagram, within the sum-over-essential states approach, we observed strong qualitative and quantitative correlation between experimental and theoretical results.

Effect of Solvent-Induced Coil to Helix Conformational Change on the Two-Photon Absorption Spectrum of Poly(3,6-phenanthrene)

This paper investigates the effect of solvent-induced conformational changes of poly(3,6-phenanthrene) on their two-photon absorption (2PA). Such effect was studied employing the wavelength-tunable femtosecond Z-scan technique and modeled using the sum-over-essential states approach. We observed a strong reduction of the 2PA cross-section when the sample was prepared in hexane (poor solvent) in comparison to chloroform (good solvent), which is related to the conformation adopted by the polymer in each case. In chloroform it adopts a random coil conformation, as opposed to the one-handed helix conformation in hexane. Our results pointed out that the coil to helix conformation change decreases the degree of molecular planarity of the polymer pi-conjugated backbone, which is primarily responsible for their optical nonlinearity, contributing to diminishing the effective transition dipole moments and, consequently, the 2PA cross-section. Moreover, by studying the nonlinear response with different light polarization, we showed that, although the solvent-induced conformational change does not alter the molecular symmetry of the polymer, it modifies considerably the direction of the transition dipole moments between the excited states.

Observation of Direct-Photon Collective Flow in Au plus Au Collisions at root s(NN)=200 GeV

The second Fourier component v(2) of the azimuthal anisotropy with respect to the reaction plane is measured for direct photons at midrapidity and transverse momentum (p(T)) of 1-12 GeV/c in Au + Au collisions at root s(NN) = 200 GeV. Previous measurements of this quantity for hadrons with p(T) < 6 GeV/c indicate that the medium behaves like a nearly perfect fluid, while for p(T) > 6 GeV/c a reduced anisotropy is interpreted in terms of a path-length dependence for parton energy loss. In this measurement with the PHENIX detector at the Relativistic Heavy Ion Collider we find that for p(T) > 4 GeV/c the anisotropy for direct photons is consistent with zero, which is as expected if the dominant source of direct photons is initial hard scattering. However, in the p(T) < 4 GeV/c region dominated by thermal photons, we find a substantial direct-photon v(2) comparable to that of hadrons, whereas model calculations for thermal photons in this kinematic region underpredict the observed v(2).

The Role of Molecular Conformation and Polarizable Embedding for One- and Two-Photon Absorption of Disperse Orange 3 in Solution

Solvent effects on the one- and two-photon absorption (IPA and 2PA) of disperse orange 3 (DO3) in dimethyl sulfoxide (DMSO) are studied using a discrete polarizable embedding (PE) response theory. The scheme comprises a quantum region containing the chromophore and an atomically granulated classical region for the solvent accounting for full interactions within and between the two regions. Either classical molecular dynamics (MD) or hybrid Car-Parrinello (CP) quantum/classical (QM/MM) molecular dynamics simulations are employed to describe the solvation of DO3 in DMSO, allowing for an analysis of the effect of the intermolecular short-range repulsion, long-range attraction, and electrostatic interactions on the conformational changes of the chromophore and also the effect of the solute-solvent polarization. PE linear response calculations are performed to verify the character, solvatochromic shift, and overlap of the two lowest energy transitions responsible for the linear absorption spectrum of DO3 in DMSO in the visible spectral region. Results of the PE linear and quadratic response calculations, performed using uncorrelated solute-solvent configurations sampled from either the classical or hybrid CP QM/MM MD simulations, are used to estimate the width of the line shape function of the two electronic lowest energy excited states, which allow a prediction of the 2PA cross-sections without the use of empirical parameters. Appropriate exchange-correlation functionals have been employed in order to describe the charge-transfer process following the electronic transitions of the chromophore in solution.

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.

Direct photon production in p plus p collisions at root s=200 GeV at midrapidity

The differential cross section for the production of direct photons in p + p collisions at root s = 200 GeV at midrapidity was measured in the PHENIX detector at the Relativistic Heavy Ion Collider. Inclusive direct photons were measured in the transverse momentum range from 5: 5-25 GeV/c, extending the range beyond previous measurements. Event structure was studied with an isolation criterion. Next-to-leading-order perturbative-quantum-chromodynamics calculations give a good description of the spectrum. When the cross section is expressed versus x(T), the PHENIX data are seen to be in agreement with measurements from other experiments at different center-of-mass energies.

On reducing test length for FSMs with extra states

A long-standing problem when testing from a deterministic finite state machine is to guarantee full fault coverage even if the faults introduce extra states in the implementations. It is well known that such tests should include the sequences in a traversal set which contains all input sequences of length defined by the number of extra states. This paper suggests the SPY method, which helps reduce the length of tests by distributing sequences of the traversal set and reducing test branching. It is also demonstrated that an additional assumption about the implementation under test relaxes the requirement of the complete traversal set. The results of the experimental comparison of the proposed method with an existing method indicate that the resulting reduction can reach 40%. Experimental results suggest that the additional assumption about the implementation can help in further reducing the test suite length. Copyright (C) 2011 John Wiley & Sons, Ltd.

The peculiar isolated neutron star in the Carina Nebula Deep XMM-Newton and ESO-VLT observations of 2XMM J104608.7-594306

While fewer in number than the dominant rotation-powered radio pulsar population, peculiar classes of isolated neutron stars (INSs) which include magnetars, the ROSAT-discovered "Magnificent Seven" (M7), rotating radio transients (RRATs), and central compact objects in supernova remnants (CCOs) - represent a key element in understanding the neutron star phenomenology. We report the results of an observational campaign to study the properties of the source 2XMM J104608.7-594306, a newly discovered thermally emitting INS. The evolutionary state of the neutron star is investigated by means of deep dedicated observations obtained with the XMM-Newton Observatory, the ESO Very Large Telescope, as well as publicly available gamma-ray data from the Fermi Space Telescope and the AGILE Mission. The observations confirm previous expectations and reveal a unique type of object. The source, which is likely within the Carina Nebula (N-H = 2.6x10(21) cm(-2)), has a spectrum that is both thermal and soft, with kT(infinity) = 135 eV. Non-thermal (magnetospheric) emission is not detected down to 1% (3 sigma, 0.1-12 keV) of the source luminosity. Significant deviations (absorption features) from a simple blackbody model are identified in the spectrum of the source around energies 0.6 keV and 1.35 keV. While the former deviation is likely related to a local oxygen overabundance in the Carina Nebula, the latter can only be accounted for by an additional spectral component, which is modelled as a Gaussian line in absorption with EW = 91 eV and sigma = 0.14 keV (1 sigma). Furthermore, the optical counterpart is fainter than m(V) = 27 (2 sigma) and no gamma-ray emission is significantly detected by either the Fermi or AGILE missions. Very interestingly, while these characteristics are remarkably similar to those of the M7 or the only RRAT so far detected in X-rays, which all have spin periods of a few seconds, we found intriguing evidence of very rapid rotation, P = 18.6ms, at the 4 sigma confidence level. We interpret these new results in the light of the observed properties of the currently known neutron star population, in particular those of standard rotation-powered pulsars, recycled objects, and CCOs. We find that none of these scenarios can satisfactorily explain the collective properties of 2XMM J104608.7-594306, although it may be related to the still poorly known class of Galactic anti-magnetars. Future XMM-Newton data, granted for the next cycle of observations (AO11), will help us to improve our current observational interpretation of the source, enabling us to significantly constrain the rate of pulsar spin down.

Deviation from quark number scaling of the anisotropy parameter v(2) of pions, kaons, and protons in Au+Au collisions at root s(NN)=200 GeV

Measurements of the anisotropy parameter v(2) of identified hadrons (pions, kaons, and protons) as a function of centrality, transverse momentum p(T), and transverse kinetic energy KET at midrapidity (vertical bar eta vertical bar < 0.35) in Au + Au collisions at root s(N N) = 200 GeV are presented. Pions and protons are identified up to p(T) = 6 GeV/c, and kaons up to p(T) = 4 GeV/c, by combining information from time-of-flight and aerogel Cerenkov detectors in the PHENIX Experiment. The scaling of v(2) with the number of valence quarks (n(q)) has been studied in different centrality bins as a function of transverse momentum and transverse kinetic energy. A deviation from previously observed quark-number scaling is observed at large values of KET/n(q) in noncentral Au + Au collisions (20-60%), but this scaling remains valid in central collisions (0-10%).

Phylogenetic relation among bovine rabies cases from Minas Gerais and Sao Paulo States, Brazil: a possible common origin

Acknowledgements: CAPES, FAPESP process number 2011/06236-0

The Emergence of the Post-Socialist Welfare State - The Case of the Baltic States : Estonia, Latvia and Lithuania

This dissertation takes a step towards providing a better understanding of post-socialist welfare state development from a theoretical as well as an empirical perspective. The overall analytical goal of this thesis has been to critically assess the development of social policies in Estonia, Latvia and Lithuania using them as illustrative examples of post-socialist welfare state development in the light of the theories, approaches and typologies that have been developed to study affluent capitalist democracies. The four studies included in this dissertation aspire to a common aim in a number of specific ways. The first study tries to place the ideal-typical welfare state models of the Baltic States within the well-known welfare state typologies. At the same time, it provides a rich overview of the main social security institutions in the three countries by comparing them with each other and with the previous structures of the Soviet period. It examines the social insurance institutions of the Baltic States (old-age pensions, unemployment insurance, short-term benefits, sickness, maternity and parental insurance and family benefits) with respect to conditions of eligibility, replacement rates, financing and contributions. The findings of this study indicate that the Latvian social security system can generally be labelled as a mix of the basic security and corporatist models. The Estonian social security system can generally also be characterised as a mix of the basic security and corporatist models, even if there are some weak elements of the targeted model in it. It appears that the institutional changes developing in the social security system of Lithuania have led to a combination of the basic security and targeted models of the welfare state. Nevertheless, as the example of the three Baltic States shows, there is diversity in how these countries solve problems within the field of social policy. In studying the social security schemes in detail, some common features were found that could be attributed to all three countries. Therefore, the critical analysis of the main social security institutions of the Baltic States in this study gave strong supporting evidence in favour of identifying the post-socialist regime type that is already gaining acceptance within comparative welfare state research. Study Two compares the system of social maintenance and insurance in the Soviet Union, which was in force in the three Baltic countries before their independence, with the currently existing social security systems. The aim of the essay is to highlight the forces that have influenced the transformation of the social policy from its former highly universal, albeit authoritarian, form, to the less universal, social insurance-based systems of present-day Estonia, Latvia and Lithuania. This study demonstrates that the welfare–economy nexus is not the only important factor in the development of social programs. The results of this analysis revealed that people's attitudes towards distributive justice and the developmental level of civil society also play an important part in shaping social policies. The shift to individualism in people’s mentality and the decline of the labour movement, or, to be more precise, the decline in trade union membership and influence, does nothing to promote the development of social rights in the Baltic countries and hinders the expansion of social policies. The legacy of the past has been another important factor in shaping social programs. It can be concluded that social policy should be studied as if embedded not only in the welfare-economy nexus, but also in the societal, historical and cultural nexus of a given society. Study Three discusses the views of the state elites on family policy within a wider theoretical setting covering family policy and social policy in a broader sense and attempts to expand this analytical framework to include other post-socialist countries. The aim of this essay is to explore the various views of the state elites in the Baltics concerning family policy and, in particular, family benefits as one of the possible explanations for the observed policy differences. The qualitative analyses indicate that the Baltic States differ significantly with regard to the motives behind their family policies. Lithuanian decision-makers seek to reduce poverty among families with children and enhance the parents’ responsibility for bringing up their children. Latvian policy-makers act so as to increase the birth rate and create equal opportunities for children from all families. Estonian policy-makers seek to create equal opportunities for all children and the desire to enhance gender equality is more visible in the case of Estonia in comparison with the other two countries. It is strongly arguable that there is a link between the underlying motives and the kinds of family benefits in a given country. This study, thus, indicates how intimately the attitudes of the state bureaucrats, policy-makers, political elite and researchers shape social policy. It confirms that family policy is a product of the prevailing ideology within a country, while the potential influence of globalisation and Europeanisation is detectable too. The final essay takes into account the opinions of welfare users and examines the performances of the institutionalised family benefits by relying on the recipients’ opinions regarding these benefits. The opinions of the populations as a whole regarding government efforts to help families are compared with those of the welfare users. Various family benefits are evaluated according to the recipients' satisfaction with those benefits as well as the contemporaneous levels of subjective satisfaction with the welfare programs related to the absolute level of expenditure on each program. The findings of this paper indicate that, in Latvia, people experience a lower level of success regarding state-run family insurance institutions, as compared to those in Lithuania and Estonia. This is deemed to be because the cash benefits for families and children in Latvia are, on average, seen as marginally influencing the overall financial situation of the families concerned. In Lithuania and Estonia, the overwhelming majority think that the family benefit systems improve the financial situation of families. It appears that recipients evaluated universal family benefits as less positive than targeted benefits. Some universal benefits negatively influenced the level of general satisfaction with the family benefits system provided in the countries being researched. This study puts forward a discussion about whether universalism is always more legitimate than targeting. In transitional economies, in which resources are highly constrained, some forms of universal benefits could turn out to be very expensive in relative terms, without being seen as useful or legitimate forms of help to families. In sum, by closely examining the different aspects of social policy, this dissertation goes beyond the over-generalisation of Eastern European welfare state development and, instead, takes a more detailed look at what is really going on in these countries through the examples of Lithuania, Latvia and Estonia. In addition, another important contribution made by this study is that it revives ‘western’ theoretical knowledge through ‘eastern’ empirical evidence and provides the opportunity to expand the theoretical framework for post-socialist societies.

Probing unoccupied electronic states in aqueous solutions

Water is one of the most common compounds on earth and is essential for all biological activities. Water has, however, been a mystery for many years due to the large number of unusual chemical and physical properties, e.g. decreased volume during melting and maximum density at 4 °C. The origin of the anomalies behavior is the nature of the hydrogen bond. This thesis will presented an x-ray absorption spectroscopy (XAS) study to reveal the hydrogen bond structure in liquid water. The x-ray absorption process is faster than a femtosecond and thereby reflects the molecular orbital structure in a frozen geometry locally around the probed water molecules. The results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms. The molecular arrangement in the first coordination shell of liquid water is actually very similar as the two-hydrogen-bonded configurations at the surface of ice. This discovery suggests that most molecules in liquid water have two-hydrogen-bonded configurations with one donor and one acceptor hydrogen bond compared to the four-hydrogen-bonded tetrahedral structure in ice. This result is controversial since the general picture is that the structure of liquid water is very similar to the structure of ice. The results are, however, consistent with x-ray and neutron diffraction data but reveals serious discrepancies with structures based on current molecular dynamics simulations. The two-hydrogen-bond configuration in liquid water is rigid and heating from 25 °C to 90 °C introduce a minor change in the hydrogen-bonded configurations. Furthermore, XAS studies of water in aqueous solutions show that ion hydration does not affect the hydrogen bond configuration of the bulk. Only water molecules in the close vicinity to the ions show changes in the hydrogen bond formation. XAS data obtained with fluorescence yield are sensitive enough to resolved electronic structure of water molecules in the first hydration sphere and to distinguish between different protonated species. Hence, XAS is a useful tool to provide insight into the local electronic structure of a hydrogen-bonded liquid and it is applied for the first time on water revealing unique information of high importance.

The secondary market for life insurance policies in the United States market evolution and product valuation

In this work we discuss the secondary market for life insurance policies in the United States of America. First, we give an overview of the life settlement market: how it came into existence, its growth prospects and the ethical issues it arises. Secondly, we discuss the characteristics of the different life insurance products present in the market and describe how life settlements are originated. Life settlement transactions tend to be long and complex transactions that require the involvement of a number of parties. Also, a direct investment into life insurance policies is fraught with a number of practical issues and entails risks that are not directly related to longevity. This may reduce the efficiency of a direct investment in physical policies. For these reasons, a synthetic longevity market has evolved. The number of parties involved in a synthetic longevity transaction is typically smaller and the broker-dealer transferring the longevity exposure will be retaining most or all of the risks a physical investment entails. Finally, we describe the main methods used in the market to evaluate life settlement investments and the role of life expectancy providers.

Time-of-flight two-photon photoemission spectromicroscopy with femtosecond laser radiation

Time-of-flight photoemission spectromicroscopy was used to measure and compare the two-photon photoemission (2PPE) spectra of Cu and Ag nanoparticles with linear dimensions ranging between 40 nm and several 100 nm, with those of the corresponding homogeneous surfaces. 2PPE was induced employing femtosecond laser radiation from a frequency-doubled Ti:sapphire laser in the spectral range between 375 nm and 425 nm with a pulse width of 200 fs and a repetition rate of 80 MHz. The use of a pulsed radiation source allowed us to use a high-resolution photoemission electron microscope as imaging time-of-flight spectrometer, and thus to obtain spectroscopic information about the laterally resolved electron signal. Ag nanoparticle films have been deposited on Si(111) by electron-beam evaporation, a technique leading to hemispherically-shaped Ag clusters. Isolated Cu nanoparticles have been generated by prolonged heating of a polycrystalline Cu sample. If compared to the spectra of the corresponding homogeneous surfaces, the Cu and Ag nanoparticle spectra are characterized by a strongly enhanced total 2PPE yield (enhancement factor up to 70), by a shift (about 0.1 eV) of the Fermi level onset towards lower final state energies, by a reduction of the work function (typically by 0.2 eV) and by a much steeper increase of the 2PPE yield towards lower final state energies. The shift of the Fermi level onset in the nanoparticle spectra has been explained by a positive unit charge (localized photohole) residing on the particle during the time-scale relevant for the 2PPE process (few femtoseconds). The total 2PPE yield enhancement and the different overall shape of the spectra have been explained by considering that the laser frequency was close to the localized surface plasmon resonance of the Cu and Ag nanoparticles. The synchronous oscillations induced by the laser in the metal electrons enhance the near-zone (NZ) field, defined as the linear superposition of the laser field and the field produced in the vicinity of the particles by the forced charge oscillations. From the present measurements it is clear that the NZ field behavior is responsible for the 2PPE enhancement and affects the 2PPE spatial and energy distribution and its dynamics. In particular, its strong spatial dependence allows indirect transitions through real intermediate states to take place in the metal clusters. Such transitions are forbidden by momentum conservation arguments and are thus experimentally much less probable on homogeneous surfaces. Further, we investigated specially tailored moon-shaped small metal nanostructures, whose NZ field was theoretically predicted, and compared the calculation with the laterally resolved 2PPE signal. We could show that the 2PPE signal gives a clear fingerprint of the theoretically predicted spatial dependence of the NZ field. This potential of our method is highly attractive in the novel field of plasmonics.

Resonanzionisations-Massenspektrometrie mit gepulsten und kontinuierlichen Lasern an Plutonium

Zusammenfassung Zur Weiterentwicklung derResonanzionisations-Massenspektrometrie (RIMS) für dieUltra-Spurenanalyse von Plutonium wurde im Rahmen dieserArbeit eine neue RIMS-Apparatur konzipiert und aufgebaut.Erstmals wurden bei der spektroskopischen Untersuchung vonPlutonium schmalbandige kontinuierliche Laser verwendet. Eswurdenumfangreiche Messreihen durchgeführt, um denResonanzionisationsprozess von Plutonium mit kontinuierlichenLasern zuspezifizieren und möglichst effiziente Anregungsleitern für dieResonanzionisation zu ermitteln. Ein maßgeblicherBestandteil derExperimente war in diesem Zusammenhang die Untersuchung vonautoionisierenden Zuständen. Für die zwei bestenAnregungsleiternwurden Sättigungsintensitäten, Linienbreiten sowieHyperfeinstruktur- und Isotopeneffekte vermessen. Mit denErkenntnissen aus diesen Voruntersuchungen konnten genaueIsotopenverhältnisbestimmungen durchgeführt werden. DieEffizienzdes Gesamtsystems wurde mit Hilfe von synthetischen Probenbestimmt. Alle Messungen wurden wegen der hohen Aktivität undRadiotoxizität von Plutonium mit vergleichsweise geringenTeilchenzahlen durchgeführt. Unterschiedliche Laserionisationsverfahren mit kontinuierlicheroder/und gepulster Laseranregung wurden hinsichtlich ihrerrelativen Effizienz und Selektivität direkt miteinanderverglichen. Weiterhin wurde ein sehr effizientes drei-Stufen, zwei-FarbenAnregungsschema für die gepulste Resonanzionisation vonPlutoniumuntersucht, welches u. a. auf einem Zwei-Photonenübergang ineinenautoionisierenden Zustand beruht. Schließlich wurden mit demetablierten RIMS-Verfahren eine Vielzahl von Umweltmessungendurchgeführt und es wurde an der Weiterentwicklung und derQualitätssicherung des Verfahrens gearbeitet.