Influence of cooperativity on the frequency shift of the Ar–H stretch vibration in HArF complexes

CH₃Li–FArH–X (X?=?H₂, OC, N₂, P₂, CO₂, CO, BeH₂) trimers have been investigated using quantum chemical calculations at the QCISD/6-311++G(2d,2p) level. The results show that the lithium bonding has a prominent effect on the strength and properties of the hydrogen bonding. The hydrogen-bonding interaction energy is increased by 160–340% due to the presence of lithium bonding. The Ar–H stretch vibration shows a blue shift in the FArH–X (X?=?H₂, OC, N₂, CO₂, CO) dimer, but a red shift in the FArH–X (X?=?P₂, BeH₂) dimer. The red shift is increased in the corresponding trimer, while the blue shift shows a different change. The blue shift is also increased in CH₃Li–FArH–X (X?=?H₂, OC, N₂, CO₂) trimers, but it changes to a red shift in the CH₃Li–FArH–CO trimer. The shift change is consistent with the explanation given by Joseph and Jemmis.     

High-resolution,near-infrared CW-CRDS,and ab initio investigations of N2O–HDO

We have investigated the N₂O–HDO molecular complex using ab initio calculations at the CCSD(T)-F12a/aug-cc-pVTZ level of theory and using cavity ring-down spectroscopy to probe an HDO/N₂O/Ar supersonic jet around 1.58 μm. A single a-type vibrational band was observed, 13 cm^?1 redshifted compared to the OH+OD excited band in HDO, and 173 vibration-rotation lines were assigned (T_rot ≈ 20 K). A weighted fit of existing microwave and present near infrared (NIR) data was achieved using a standard Watson's Hamiltonian (σ = 1.26), producing ground and excited states rotational constants. The comparison of the former with those calculated ab initio suggests a planar geometry in which the OD rather than the OH bond in water is almost parallel to NNO. The equilibrium geometry and dissociation energy (D_e = –11.7 kJ/mol) of the water–nitrous oxide complex were calculated. The calculations further demonstrate and allow characterising another minimum, 404 cm^?1 (ΔE₀) higher in energy. Harmonic vibrational frequencies and dissociation energies, D₀, were calculated for various conformers and isotopic forms of the complex, in both minima. The absence of N₂O–D₂O from dedicated NIR experiments is reported and discussed.     

Theory studies of the local lattice distortions and the EPR parameters for Cu2+, Mn2+ and Fe3+ centres in ZnWO4

The local lattice distortions and the electron paramagnetic resonance (EPR) parameters (g factors, hyperfine structure constants and zero-field splittings) for Cu²⁺, Mn²⁺ and Fe³⁺ in ZnWO₄ are theoretically studied based on the perturbation calculations for rhombically elongated octahedral 3d⁹ and 3d⁵ complexes. The impurity centres on Zn²⁺ sites undergo the local elongations of 0.01, 0.002 and 0.013 Å along the C₂ axis and the planar bond angle variations of 8.1°, 8.0° and 8.6° for Cu²⁺, Mn²⁺ and Fe³⁺, respectively, due to the Jahn–Teller effect and size and charge mismatch. In contrast to the host Zn²⁺ site with obvious axial elongation (～0.31 Å) and perpendicular (angular) rhombic distortion, all the impurity centres demonstrate more regular octahedral due to the above local lattice distortions. The copper centre exhibits significant Jahn–Teller reductions for the spin-orbit coupling and orbital angular momentum interactions, characterised by the Jahn–Teller reduction factor J (≈0.29 ? 1). The calculated EPR parameters agree well with the experimental results. The local structures of the impurity centres are analysed in view of the corresponding lattice distortions.     

Simulation of pedestrian counter flow through bottlenecks by using an agent-based model

Considerable research has been conducted on the topic of unidirectional evacuations from exits. However, few studies aim at simulating counter flow through a bottleneck with complex conflict. This paper proposes an agent-based model to investigate bidirectional flow evacuation. Pedestrian speed is determined by the speed of the leading agent and the surrounding agents. The moving direction of pedestrian originates from four forces, namely, gradient force, repulsive force, resistance force, and random force. These four forces dominate the main stream of the pedestrian moving trajectory, the interaction between pedestrians and their local environment, the resistance or disinclination to movement, and the random variations and chaotic nature of pedestrian dynamics. The novelty of this research is in the agent-based model that combines the agent and forces while providing insights for the simulation of the pedestrian dynamic on the cognitive level. The experiment results show that the behavior that arises from this model is consistent with the observations from Guangzhou Metro and that this model could help capture the essence of pedestrian behavior near egresses.     

A modular attachment mechanism for software network evolution

A modular attachment mechanism of software network evolution is presented in this paper. Compared with the previous models, our treatment of object-oriented software system as a network of modularity is inherently more realistic. To acquire incoming and outgoing links in directed networks when new nodes attach to the existing network, a new definition of asymmetric probabilities is given. Based on this, modular attachment instead of single node attachment in the previous models is then adopted. The proposed mechanism is demonstrated to be able to generate networks with features of power-law, small-world, and modularity, which represents more realistic properties of actual software networks. This work therefore contributes to a more accurate understanding of the evolutionary mechanism of software systems. What is more, explorations of the effects of various software development principles on the structure of software systems have been carried out, which are expected to be beneficial to the software engineering practices.     

Detecting community structure using label propagation with weighted coherent neighborhood propinquity

Community detection has become an important methodology to understand the organization and function of various real-world networks. The label propagation algorithm (LPA) is an almost linear time algorithm proved to be effective in finding a good community structure. However, LPA has a limitation caused by its one-hop horizon. Specifically, each node in LPA adopts the label shared by most of its one-hop neighbors; much network topology information is lost in this process, which we believe is one of the main reasons for its instability and poor performance. Therefore in this paper we introduce a measure named weighted coherent neighborhood propinquity (weighted-CNP) to represent the probability that a pair of vertices are involved in the same community. In label update, a node adopts the label that has the maximum weighted-CNP instead of the one that is shared by most of its neighbors. We propose a dynamic and adaptive weighted-CNP called entropic-CNP by using the principal of entropy to modulate the weights. Furthermore, we propose a framework to integrate the weighted-CNP in other algorithms in detecting community structure. We test our algorithm on both computer-generated networks and real-world networks. The experimental results show that our algorithm is more robust and effective than LPA in large-scale networks.     

Community detection in complex networks by density-based clustering

We proposed a method to find the community structure in a complex network by density-based clustering. Physical topological distance is introduced in density-based clustering for determining a distance function of specific influence functions. According to the distribution of the data, the community structures are uncovered. The method keeps a better connection mode of the community structure than the existing algorithms in terms of modularity, which can be viewed as a basic characteristic of community detection in the future. Moreover, experimental results indicate that the proposed method is efficient and effective to be used for community detection of medium and large networks.     

Mechanism of disease in early osteoarthritis: application of modern MR imaging techniques — a technical report

The application of biomolecular magnetic resonance imaging becomes increasingly important in the context of early cartilage changes in degenerative and inflammatory joint disease before gross morphological changes become apparent. In this limited technical report, we investigate the correlation of MRI T1, T2 and T1ρ relaxation times with quantitative biochemical measurements of proteoglycan and collagen contents of cartilage in close synopsis with histologic morphology. A recently developed MRI sequence, T1ρ, was able to detect early intracartilaginous degeneration quantitatively and also qualitatively by color mapping demonstrating a higher sensitivity than standard T2-weighted sequences. The results correlated highly with reduced proteoglycan content and disrupted collagen architecture as measured by biochemistry and histology. The findings lend support to a clinical implementation that allows rapid visual capturing of pathology on a local, millimeter level. Further information about articular cartilage quality otherwise not detectable in vivo, via normal inspection, is needed for orthopedic treatment decisions in the present and future.