Analysis of some reaction pathways active during cyclopentadiene pyrolysis

The cyclopentadienyl radical (cC(5)H(5)) is among the most stable radical species that can be generated during the combustion and pyrolysis of hydrocarbons and it is generally agreed that its contribution to the gas phase reactivity is significant. In this study the kinetics of one key cC(5)H(5) reaction channel, namely the reaction between cC(5)H(5) and cyclopentadiene (cC(5)H(6)), was investigated using ab initio calculations and RRKM/Master Equation theory. It was found that most of the excited C(5)H(5)_C(5)H(6) adducts formed by the addition of cC(5)H(5) to cC(5)H(6) decompose back to reactants and that the major reaction products are, in order of importance, indene, vinylfulvene (a most probable styrene precursor), phenylbutadiene, and benzene. The preferred reaction pathway of the C(5)H(5)_C(5)H(6) adduct is started by the migration of the tertiary hydrogen of the C(5)H(5) ring to a vicinal carbon and followed by the β-opening of the C(5)H(6) ring, which is the rate determining step. Successive molecular rearrangements lead to decomposition to the four possible products. The kinetic constants for the four reaction channels, calculated at atmospheric pressure and interpolated in cm(3) mol(-1) s(-1) between 900 and 2000 K, are k(indene) = 10(25.197)T(-3.935)?exp(-11630/T(K)), k(vinylfulvene) = 10(65.077)T(-14.20)?exp(-37567/T(K)), k(benzene) = 10(29.172)T(-4.515)?exp(-20570/T(K)), and k(phenylbutadiene) = 10(16.743)T(-1.407)?exp(-11804/T(K)). The predictive capability of the reaction set so determined was tested through the simulations of recent cC(5)H(6) pyrolysis and combustion experiments using a detailed kinetic mechanism. A quantitative agreement with experimental data was obtained by assuming that vinylfulvene converts rapidly to stryrene, increasing its reaction channel by a factor of 2, and assuming that phenylbutadiene rapidly decomposes with equal probability to styrene and benzene.     

The Beneficial Role of Random Strategies in Social and Financial Systems

In this paper we focus on the beneficial role of random strategies in social sciences by means of simple mathematical and computational models. We briefly review recent results obtained by two of us in previous contributions for the case of the Peter principle and the efficiency of a Parliament. Then, we develop a new application of random strategies to the case of financial trading and discuss in detail our findings about forecasts of markets dynamics.     

Emergent Newtonian dynamics and the geometric origin of mass

We consider a set of macroscopic (classical) degrees of freedom coupled to an arbitrary many-particle Hamiltonian system, quantum or classical. These degrees of freedom can represent positions of objects in space, their angles, shape distortions, magnetization, currents and so on. Expanding their dynamics near the adiabatic limit we find the emergent Newton’s second law (force is equal to the mass times acceleration) with an extra dissipative term. In systems with broken time reversal symmetry there is an additional Coriolis type force proportional to the Berry curvature. We give the microscopic definition of the mass tensor. The mass tensor is related to the non-equal time correlation functions in equilibrium and describes the dressing of the slow degree of freedom by virtual excitations in the system. In the classical (high-temperature) limit the mass tensor is given by the product of the inverse temperature and the Fubini–Study metric tensor determining the natural distance between the eigenstates of the Hamiltonian. For free particles this result reduces to the conventional definition of mass. This finding shows that any mass, at least in the classical limit, emerges from the distortions of the Hilbert space highlighting deep connections between any motion (not necessarily in space) and geometry. We illustrate our findings with four simple examples.     

Freudenthal duality and generalized special geometry

Freudenthal duality, introduced in Borsten et al. (2009) [1] and defined as an anti-involution on the dyonic charge vector in d=4 space-time dimensions for those dualities admitting a quartic invariant, is proved to be a symmetry not only of the classical Bekenstein-Hawking entropy but also of the critical points of the black hole potential.Furthermore, Freudenthal duality is extended to any generalized special geometry, thus encompassing all N>2 supergravities, as well as N=2 generic special geometry, not necessarily having a coset space structure.     

Statistical approach to the analysis of cell desynchronization data

Experimental measurements on semi-synchronous tumor cell populations show that after a few cell cycles they desynchronize completely, and this desynchronization reflects the intercell variability of cell-cycle duration. It is important to identify the sources of randomness that desynchronize a population of cells living in a homogeneous environment: for example, being able to reduce randomness and induce synchronization would aid in targeting tumor cells with chemotherapy or radiotherapy. Here we describe a statistical approach to the analysis of the desynchronization measurements that is based on minimal modeling hypotheses, and can be derived from simple heuristics. We use the method to analyze existing desynchronization data and to draw conclusions on the randomness of cell growth and proliferation.     

Determination of continuous variable entanglement by purity measurements

We classify the entanglement of two-mode Gaussian states according to their degree of total and partial mixedness. We derive exact bounds that determine maximally and minimally entangled states for fixed global and marginal purities. This characterization allows for an experimentally reliable estimate of continuous variable entanglement based on measurements of purity.     

Dye solar cells efficiency maps: a parametric study

In this work we present a numerical simulation of a dye solar cell efficiency using a drift-diffusion model for the complete cell. The physical parameters such as the active layer thickness, the electron mobility and the dye spectrum are varied systematically in a range of values individuated experimentally, in order to obtain efficiency maps that reveal interesting features in this kind of devices.     

Principal components and spatial patterns of rain over Northern Italy, in relation to wind and geopotential fields

Summary A statistical study of precipitation over the Po Valley and the Alps during four winters, based on the application of a principal component (p.c.) method, exhibited a good correlation between the first three rotated eigenvectors of the cross-product matrix (between time series of data recorded at 70 stations) and three typical atmospheric circulation schemes over Northern Italy. The study is here continued, by relating these results to meteorological fields evaluated over a region wider than the area previously considered. Our attention mainly concentrated on the fields of time trend of geopotential height at 850 hPa over Europe, between latitude 34.5 and 51 degrees North and longitudes 0 and 21 degrees East. This was suggested by some peculiar relationships shown by the statistical distributions of geopotential height and wind direction and speed with respect to the first three p.c.’s. These relationships made us think of the possibility to use those trends as predictors of precipitation fields. Our analysis puts into evidence that three spatial patterns of geopotential, height time trend can be safely associated to the first three p.c.’s and, as a consequence, to the three precipitation modes corresponding to the spatial distributions of the eigenvectors, previously identified by us. They can therefore be considered meaningful precursors of precipitation field patterns over Northern Italy and Alpine regions.

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Riassunto Uno studio statistico della precipitazione sulla pianura padana e sulle Alpi durante quattro inverni, basato sull’applicazione del metodo delle componenti principali (c.p.), ha mostrato una buona correlazione fra i primi tre autovettori rotati della matrice dei prodotti incrociati (fra le serie temporali dei dati registrati in 70 stazioni) e tre tipici schemi di circolazione atmosferica sull’Italia del Nord. Lo studio viene qui prosequito, mettendo in relazione tali risultati con campi meteorologici valutati su una zona piú ampia di quella precedentemente considerata. La nostra attenzione si è prevalentemente concentrata sui campi di tendenza temporale dell’altezza di geopotenziale a 850 hPa sull’Europa, a latitudini comprese tra 34.5 e 51 gradi Nord e longitudini fra 0 e 21 gradi Est. Ciò è stato suggerito da alcune relazioni peculiari mostrate dalle distribuzioni statistiche di altezza di geopotenziale e di direzione ed intensità del vento rispetto alle prime tre c.p., che ci hanno fatto pensare alla possibilità di usare tali tendenze come predittori del campo di precipitazione. La nostra analisi ha messo in evidenza il fatto che tre distribuzioni spaziali di tendenza temporale del campo di altezza di geopotenziale possono essere con sicurezza associate alle prime tre c.p. e., quindi, ai tre modi di precipitazione corrispondenti alle distribuzioni spaziali degli autovettori precedentemente da noi identificati. Essi possono pertanto essere considerati significativi precursori del campo di precipitazione sull’Italia del Nord e sulle regioni alpine.

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Резюме Статистическое исследование выпадения осадков над долиной реки По и Альпами в течение четырех зим, основанное на применении метода главных компонент, обнаруживает хорошую корреляцию между первыми тремя вращающимися собственными векторами матрицы векторного произведения (между временными последовательностями данных, зарегистрированных на 70 станциях) и тремя схемами типичной атмосферной циркуляции над Северной Италией. В этой работе продолжены исследования. Полученные результаты связывайотся с метеорологическими полями, вычисленными над областью, которая шире ранее рассмотренной области. Главное внимание мы обращаем на поля временного хода для геопотенциальной высоты при 850гПа над Европой, между 34.5^щ и 51^щ северной широты и между 0^щ и 21^щ восточной долготы. Это следует из специальных соотношений, полученных с помощью статистических распределений геопотенциальной высоты и направления и скорости ветра относительно первых трех главных компонент. Эти соотношения позволяют нам использовать исследованные тенденции, как предсказатели полей вьшадения осадков. Нам анализ подтверждает, что три пространственным распределения временного хода для геопотенциальной высоты могут быть связаны с первыми тремя главными компонентами и, как следствие, с тремя моделями выцадения осадков, которые соответствуют пространственным распределениям собственных векторов, ранее идентифицированных в работе [Ш]. Следовательно, они могут рассматриватяся как предвестники для распределений полей осадков над Северной Италией и над Альпами.