The Carriers of the Interstellar Unidentified Infrared Emission Features: Constraints from the Interstellar C-H Stretching Features at 3.2-3.5 Micrometers

The unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometer, commonly attributed to polycyclic aromatic hydrocarbon (PAH) molecules, have been recently ascribed to mixed aromatic/aliphatic organic nanoparticles. More recently, an upper limit of <9% on the aliphatic fraction (i.e., the fraction of carbon atoms in aliphatic form) of the UIE carriers based on the observed intensities of the 3.4 and 3.3 micrometer emission features by attributing them to aliphatic and aromatic C-H stretching modes, respectively, and assuming A_34./A_3.3~0.68 derived from a small set of aliphatic and aromatic compounds, where A_3.4 and A_3.3 are respectively the band strengths of the 3.4 micrometer aliphatic and 3.3 micrometer aromatic C-H bonds. To improve the estimate of the aliphatic fraction of the UIE carriers, here we analyze 35 UIE sources which exhibit both the 3.3 and 3.4 micrometer C-H features and determine I_3.4/I_3.3, the ratio of the power emitted from the 3.4 micrometer feature to that from the 3.3 micrometer feature. We derive the median ratio to be ~ 0.12. We employ density functional theory and second-order perturbation theory to compute A_3.4/A_3.3 for a range of methyl-substituted PAHs. The resulting A_3.4/A_3.3 ratio well exceeds 1.4, with an average ratio of ~1.76. By attributing the 3.4 micrometer feature exclusively to aliphatic C-H stretch (i.e., neglecting anharmonicity and superhydrogenation), we derive the fraction of C atoms in aliphatic form to be ~2%. We therefore conclude that the UIE emitters are predominantly aromatic.Comment: 14 pages, 5 figures, 1 table; accepted for publication in The Astrophysical Journa

ASAP : towards accurate, stable and accelerative penetrating-rank estimation on large graphs

Pervasive web applications increasingly require a measure of similarity among objects. Penetrating-Rank (P-Rank) has been one of the promising link-based similarity metrics as it provides a comprehensive way of jointly encoding both incoming and outgoing links into computation for emerging applications. In this paper, we investigate P-Rank efficiency problem that encompasses its accuracy, stability and computational time. (1) We provide an accuracy estimate for iteratively computing P-Rank. A symmetric problem is to find the iteration number K needed for achieving a given accuracy ε. (2) We also analyze the stability of P-Rank, by showing that small choices of the damping factors would make P-Rank more stable and well-conditioned. (3) For undirected graphs, we also explicitly characterize the P-Rank solution in terms of matrices. This results in a novel non-iterative algorithm, termed ASAP , for efficiently computing P-Rank, which improves the CPU time from O(n 4) to O( n 3 ). Using real and synthetic data, we empirically verify the effectiveness and efficiency of our approaches

Constrained structure of ancient Chinese poetry facilitates speech content grouping

Ancient Chinese poetry is constituted by structured language that deviates from ordinary language usage [1, 2]; its poetic genres impose unique combinatory constraints on linguistic elements [3]. How does the constrained poetic structure facilitate speech segmentation when common linguistic [4, 5, 6, 7, 8] and statistical cues [5, 9] are unreliable to listeners in poems? We generated artificial Jueju, which arguably has the most constrained structure in ancient Chinese poetry, and presented each poem twice as an isochronous sequence of syllables to native Mandarin speakers while conducting magnetoencephalography (MEG) recording. We found that listeners deployed their prior knowledge of Jueju to build the line structure and to establish the conceptual flow of Jueju. Unprecedentedly, we found a phase precession phenomenon indicating predictive processes of speech segmentation—the neural phase advanced faster after listeners acquired knowledge of incoming speech. The statistical co-occurrence of monosyllabic words in Jueju negatively correlated with speech segmentation, which provides an alternative perspective on how statistical cues facilitate speech segmentation. Our findings suggest that constrained poetic structures serve as a temporal map for listeners to group speech contents and to predict incoming speech signals. Listeners can parse speech streams by using not only grammatical and statistical cues but also their prior knowledge of the form of language

The Carriers of the "Unidentified" Infrared Emission Features: Clues from Polycyclic Aromatic Hydrocarbons with Aliphatic Sidegroups

The "unidentified" infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 $\mu$m are ubiquitously seen in various astrophysical regions. The UIE features are characteristic of the stretching and bending vibrations of aromatic hydrocarbons. The 3.3 $\mu$m feature resulting from aromatic C--H stretches is often accompanied by a weaker feature at 3.4 $\mu$m often attributed to aliphatic C--H stretches. The ratio of the observed intensity of the 3.3 $\mu$m aromatic C--H feature ($I_{3.3}$) to that of the 3.4 $\mu$m aliphatic C--H feature ($I_{3.4}$) allows one to estimate the aliphatic fraction (i.e. $N_{\rm C,aliph}/N_{\rm C,arom}$, the number of C atoms in aliphatic units to that in aromatic rings) of the UIE carriers, provided the intrinsic oscillator strengths of the 3.3 $\mu$m aromatic C--H stretch ($A_{3.3}$) and the 3.4 $\mu$m aliphatic C--H stretch ($A_{3.4}$) are known. In this article we summarize the computational results on $A_{3.3}$ and $A_{3.4}$ and their implications for the aromaticity and aliphaticity of the UIE carriers. We use density functional theory and second-order perturbation theory to derive $A_{3.3}$ and $A_{3.4}$ from the infrared vibrational spectra of seven PAHs with various aliphatic substituents (e.g., methyl-, dimethyl-, ethyl-, propyl-, butyl-PAHs, and PAHs with unsaturated alkyl-chains). The mean band strengths of the aromatic ($A_{3.3}$) and aliphatic ($A_{3.4}$) C--H stretches are derived and then employed to estimate the aliphatic fraction of the UIE carriers by comparing $A_{3.4}$/$A_{3.3}$ with $I_{3.4}$/$I_{3.3}$. We conclude that the UIE emitters are predominantly aromatic, as revealed by the observationally-derived ratio ~ 0.12 and the computationally-derived ratio ~ 1.76 which suggest an upper limit of $N_{\rm C,aliph}/N_{\rm C,arom}$ ~ 0.02 for the aliphatic fraction of the UIE carriers.Comment: 67 pages, 18 figures, 8 tables; invited article accepted for publication in "New Astronomy Review"; a considerable fraction of this article is concerned with the computational techniques and results, readers who are mainly interested in astrophysics may wish to only read "Introduction", and "Astrophysical Implications

Orientation-dependent deformation mechanisms of bcc niobium nanoparticles

Nanoparticles usually exhibit pronounced anisotropic properties, and a close insight into the atomic-scale deformation mechanisms is of great interest. In present study, atomic simulations are conducted to analyze the compression of bcc nanoparticles, and orientation-dependent features are addressed. It is revealed that surface morphology under indenter predominantly governs the initial elastic response. The loading curve follows the flat punch contact model in [110] compression, while it obeys the Hertzian contact model in [111] and [001] compressions. In plastic deformation regime, full dislocation gliding is dominated in [110] compression, while deformation twinning is prominent in [111] compression, and these two mechanisms coexist in [001] compression. Such deformation mechanisms are distinct from those in bulk crystals under nanoindentation and nanopillars under compression, and the major differences are also illuminated. Our results provide an atomic perspective on the mechanical behaviors of bcc nanoparticles and are helpful for the design of nanoparticle-based components and systems.Comment: 21 pages, 11 figure