Kinetics of the Reactions of CH2Cl, CH3CHCl, and CH3CCl2 Radicals with Cl2 in the Temperature Range 191-363 K

Peer reviewe

MDL Convergence Speed for Bernoulli Sequences

The Minimum Description Length principle for online sequence estimation/prediction in a proper learning setup is studied. If the underlying model class is discrete, then the total expected square loss is a particularly interesting performance measure: (a) this quantity is finitely bounded, implying convergence with probability one, and (b) it additionally specifies the convergence speed. For MDL, in general one can only have loss bounds which are finite but exponentially larger than those for Bayes mixtures. We show that this is even the case if the model class contains only Bernoulli distributions. We derive a new upper bound on the prediction error for countable Bernoulli classes. This implies a small bound (comparable to the one for Bayes mixtures) for certain important model classes. We discuss the application to Machine Learning tasks such as classification and hypothesis testing, and generalization to countable classes of i.i.d. models.Comment: 28 page

Isomeric states close to doubly magic 132^{132}Sn studied with JYFLTRAP

The double Penning trap mass spectrometer JYFLTRAP has been employed to measure masses and excitation energies for $11/2^-$ isomers in $^{121}$Cd, $^{123}$Cd, $^{125}$Cd and $^{133}$Te, for $1/2^-$ isomers in $^{129}$In and $^{131}$In, and for $7^-$ isomers in $^{130}$Sn and $^{134}$Sb. These first direct mass measurements of the Cd and In isomers reveal deviations to the excitation energies based on results from beta-decay experiments and yield new information on neutron- and proton-hole states close to $^{132}$Sn. A new excitation energy of 144(4) keV has been determined for $^{123}$Cd$^m$. A good agreement with the precisely known excitation energies of $^{121}$Cd$^m$, $^{130}$Sn$^m$, and $^{134}$Sb$^m$ has been found.Comment: 10 pages, 6 figures, submitted to Phys. Rev.

An aldehyde as a rapid source of secondary aerosol precursors: theoretical and experimental study of hexanal autoxidation

Aldehydes are common constituents of natural and polluted atmospheres, and their gas-phase oxidation has recently been reported to yield highly oxygenated organic molecules (HOMs) that are key players in the formation of atmospheric aerosol. However, insights into the molecular-level mechanism of this oxidation reaction have been scarce. While OH initiated oxidation of small aldehydes, with two to five carbon atoms, under high-NOx conditions generally leads to fragmentation products, longer-chain aldehydes involving an initial non-aldehydic hydrogen abstraction can be a path to molecular functionalization and growth. In this work, we conduct a joint theoretical–experimental analysis of the autoxidation chain reaction of a common aldehyde, hexanal. We computationally study the initial steps of OH oxidation at the RHF-RCCSD(T)-F12a/VDZ-F12//ωB97X-D/aug-cc-pVTZ level and show that both aldehydic (on C1) and non-aldehydic (on C4) H-abstraction channels contribute to HOMs via autoxidation. The oxidation products predominantly form through the H abstraction from C1 and C4, followed by fast unimolecular 1,6 H-shifts with rate coefficients of 1.7×10-1 and 8.6×10-1 s−1, respectively. Experimental flow reactor measurements at variable reaction times show that hexanal oxidation products including HOM monomers up to C6H11O7 and accretion products C12H22O9−10 form within 3 s reaction time. Kinetic modeling simulations including atmospherically relevant precursor concentrations agree with the experimental results and the expected timescales. Finally, we estimate the hexanal HOM yields up to seven O atoms with mechanistic details through both C1 and C4 channels.</p

Precision mass measurements of radioactive nuclei at JYFLTRAP

The Penning trap mass spectrometer JYFLTRAP was used to measure the atomic masses of radioactive nuclei with an uncertainty better than 10 keV. The atomic masses of the neutron-deficient nuclei around the N = Z line were measured to improve the understanding of the rp-process path and the SbSnTe cycle. Furthermore, the masses of the neutron-rich gallium (Z = 31) to palladium (Z = 46) nuclei have been measured. The physics impacts on the nuclear structure and the r-process paths are reviewed. A better understanding of the nuclear deformation is presented by studying the pairing energy around A = 100.Comment: 4 pages and 4 figures, RNB7 conf. pro

Mutual Information of Population Codes and Distance Measures in Probability Space

We studied the mutual information between a stimulus and a large system consisting of stochastic, statistically independent elements that respond to a stimulus. The Mutual Information (MI) of the system saturates exponentially with system size. A theory of the rate of saturation of the MI is developed. We show that this rate is controlled by a distance function between the response probabilities induced by different stimuli. This function, which we term the {\it Confusion Distance} between two probabilities, is related to the Renyi $\alpha$-Information.Comment: 11 pages, 3 figures, accepted to PR

Sequence alignment, mutual information, and dissimilarity measures for constructing phylogenies

Existing sequence alignment algorithms use heuristic scoring schemes which cannot be used as objective distance metrics. Therefore one relies on measures like the p- or log-det distances, or makes explicit, and often simplistic, assumptions about sequence evolution. Information theory provides an alternative, in the form of mutual information (MI) which is, in principle, an objective and model independent similarity measure. MI can be estimated by concatenating and zipping sequences, yielding thereby the "normalized compression distance". So far this has produced promising results, but with uncontrolled errors. We describe a simple approach to get robust estimates of MI from global pairwise alignments. Using standard alignment algorithms, this gives for animal mitochondrial DNA estimates that are strikingly close to estimates obtained from the alignment free methods mentioned above. Our main result uses algorithmic (Kolmogorov) information theory, but we show that similar results can also be obtained from Shannon theory. Due to the fact that it is not additive, normalized compression distance is not an optimal metric for phylogenetics, but we propose a simple modification that overcomes the issue of additivity. We test several versions of our MI based distance measures on a large number of randomly chosen quartets and demonstrate that they all perform better than traditional measures like the Kimura or log-det (resp. paralinear) distances. Even a simplified version based on single letter Shannon entropies, which can be easily incorporated in existing software packages, gave superior results throughout the entire animal kingdom. But we see the main virtue of our approach in a more general way. For example, it can also help to judge the relative merits of different alignment algorithms, by estimating the significance of specific alignments.Comment: 19 pages + 16 pages of supplementary materia

Challenges of Religious Literacy in Education : Islam and the Governance of Religious Diversity in Multi-faith Schools

This chapter seeks take part in an emerging research where religion is approached as a whole school endeavor. Previous research and policy recommendations typically focused on teaching about religion in school, but the accommodation of religious diversity in the wider school culture merits more attention. Based on observations in our multiple case studies, we discuss the multi-level governance of religious diversity in Finnish multi-faith schools with a particular focus on the challenges of religious literacy for educators. The three examples we present focus on the inclusion of Muslims in Finnish schools and in particular on the challenges for educator (1) in interpreting the distinction between religion and culture, (2) in recognizing and handling intra-religious diversity, and (3) in being aware of Protestant conceptions of religion and culture. A theme cutting across these examples is how they reflect the tendencies either to see different situations merely through the lens of religion (religionisation), or not to recognize the importance of religion at all (religion-blindness). We argue that religious literacy should be recognized and developed as a vital part of the intercultural competencies of educators.Peer reviewe

Q_EC values of the Superallowed beta-Emitters 10-C, 34-Ar, 38-Ca and 46-V

The Q_EC values of the superallowed beta+ emitters 10-C, 34-Ar, 38-Ca and 46-V have been measured with a Penning-trap mass spectrometer to be 3648.12(8), 6061.83(8), 6612.12(7) and 7052.44(10) keV, respectively. All four values are substantially improved in precision over previous results.Comment: 9 pages, 7 figures, 5 table