Chaotic thermal convection of couple-stress fluid layer

In this work we study the pattern of bifurcations and intermittent-chaos of non-Newtonian couple-stress shallow fluid layer subject to heating from below. The couple-stress parameter delays onset of convection, synchronizes chaotic behavior, and decreases the heat transfer . Some global aspects of the dynamics such as homoclinic bifurcations and transition to chaos are explored. The effects of particle size on the intermittent-chaos regime at particular normalized Rayleigh number, say \(r=166.1\), are investigated. With the increase in couple-stress parameter, the present Lorenz-like system synchronizes to a steady state via a series of periodic solutions interspersed with intervals of chaotic behaviors.     

Quantum discord with weak measurements

Weak measurements cause small change to quantum states, thereby opening up the possibility of new ways of manipulating and controlling quantum systems. We ask, can weak measurements reveal more quantum correlation in a composite quantum state? We prove that the weak measurement induced quantum discord, called as the “super quantum discord”, is always larger than the quantum discord captured by the strong measurement. Moreover, we prove the monotonicity of the super quantum discord as a function of the measurement strength and in the limit of strong projective measurement the super quantum discord becomes the normal quantum discord. We find that unlike the normal discord, for pure entangled states, the super quantum discord can exceed the quantum entanglement. Our results provide new insights on the nature of quantum correlation and suggest that the notion of quantum correlation is not only observer dependent but also depends on how weakly one perturbs the composite system. We illustrate the key results for pure as well as mixed entangled states.     

Nuclear Quadrupole Interactions in Nuclear Quadrupole Resonance Detection of Energetic and Controlled Materials: Theoretical Study

There has been a growing interest in nuclear quadrupole resonance (NQR) techniques useful for the detection of explosives and drugs in solid state systems. This paper uses the first-principles one-electron Hartree?CFock theoretical method to study the nuclear quadrupole interaction parameters e ² qQ and ?? for the ¹⁴N nuclei in the explosives RDX and ??-HMX as well as the drugs cocaine and heroin. It has been found in our earlier published investigations reviewed here that there is very good agreement for our calculated e ² qQ and ?? for ¹⁴N, for all these four systems, and experiment. We also present our unpublished theoretical results for cocaine with an HCl molecule attached. We successfully explain quantitatively the drastic decrease in e ² qQ in going to cocaine-HCl from cocaine-free base as well as the observed substantial increase in ?? and discuss the implications of these dramatic changes for NQR detection in general.     

Gold-catalyzed synthesis of substituted 2-aminofurans via formal [4+1]-cycloadditions on 3-en-1-ynamides

Gold-catalyzed formal [4+1]-cycloadditions between 3-en-1-ynamides 1 and 8-methylquinoline oxide are reported. The success of this reaction relies on a hypothetic oxa-Nazarov cyclization on gold-stabilized allylic cations. Preliminary results on a new 1,2-difunctionalization of 3-en-1-ynamide are also reported.     

On weighted directed graphs

The study of a mixed graph and its Laplacian matrix have gained quite a bit of interest among the researchers. Mixed graphs are very important for the study of graph theory as they provide a setup where one can have directed and undirected edges in the graph. In this article we present a more general structure, namely the weighted directed graphs and supply appropriate generalizations of several existing results for mixed graphs related to singularity of the corresponding Laplacian matrix. We also prove many new combinatorial results relating the Laplacian matrix and the graph structure.     

Ring currents in condensed ring systems

We have studied magnetism and aromaticity of polycyclic ring systems by analyzing ring currents for different circulations in these molecules. The technique employed for calculating ring currents uses correction vectors which implicitly includes all the eigenstates of the Hamiltonian in the space of the chosen configurations. We have employed the Pariser–Parr–Pople Hamiltonian and have carried out full configuration interaction (CI) calculations for small systems and approximate CI calculations for large systems. The systems studied include polyacenes, nonaromatic ring systems including the C₆₀ fragments pyracylene, fluoranthene, and corannulene, and heteroatomic systems with upto two six-membered rings. We find that in polyacenes, the aromaticity of the extreme phenyl rings reduces with increasing number of phenyl rings in the system, and it saturates at ≈⅔ the benzene value. In systems containing nonaromatic rings, we find paramagnetic or diamagnetic behavior for different circulations depending upon the number of atoms in the chosen ring cycle, in agreement with the 4n+2 rule. In corannulene, the largest fragment of C₆₀ we have studied, the five-membered ring is weakly diamagnetic while the six-membered ring is more diamagnetic, although much less than in isolated benzene. The ring structures with heteroatoms studied are pyridine, pyrimidine, and its isomers, s-triazine, quinoline and its isomer, and quinazoline and its isomers. All these have similar ring currents as in their purely carbon counterparts, although ions of these molecules show interesting behavior. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 503–513, 1998     

Regulating Charge-Transfer in Conjugated Microporous Polymers for Photocatalytic Hydrogen Evolution

Bandgap engineering in donor–acceptor conjugated microporous polymers (CMPs) is a potential way to increase the solar-energy harvesting towards photochemical water splitting. Here, the design and synthesis of a series of donor–acceptor CMPs [tetraphenylethylene (TPE) and 9-fluorenone (F) as the donor and the acceptor, respectively], F_0.1CMP , F_0.5CMP , and F_2.0CMP , are reported. These CMPs exhibited tunable bandgaps and photocatalytic hydrogen evolution from water. The donor–acceptor CMPs exhibited also intramolecular charge-transfer (ICT) absorption in the visible region (λ_max=480 nm) and their bandgap was finely tuned from 2.8 to 2.1 eV by increasing the 9-fluorenone content. Interestingly, they also showed emissions in the 540–580 nm range assisted by the energy transfer from the other TPE segments (not involved in charge-transfer interactions), as evidenced from fluorescence lifetime decay analysis. By increasing the 9-fluorenone content the emission color of the polymer was also tuned from green to red. Photocatalytic activities of the donor–acceptor CMPs ( F_0.1CMP , F_0.5CMP , and F_2.0CMP ) are greatly enhanced compared to the 9-fluorenone free polymer ( F_0.0CMP ), which is essentially due to improved visible-light absorption and low bandgap of donor–acceptor CMPs. Among all the polymers F_0.5CMP with an optimum bandgap (2.3 eV) showed the highest H₂ evolution under visible-light irradiation. Moreover, all polymers showed excellent dispersibility in organic solvents and easy coated on the solid substrates.