Theoretical and computational investigation of meta-phenylene as ferromagnetic coupler in nitronyl nitroxide diradicals

We predict the magnetic exchange coupling constant (J) for 27 m-phenylene-based nitronyl nitroxide (NN) diradicals with nine different substituents in three unique (common ortho, ortho-meta and common meta) positions on the coupler unit by using the broken-symmetry density functional methodology. For all investigated diradicals, J values are computed using B3LYP, B3LYP-D3 and M06-2X functionals with 6-311+G(d,p) basis set. The J (M06-2X) value is larger than J (B3LYP) and closer to the observed value for the unsubstituted species. Substitutions at common ortho position always produce a greater angle of twist between the spin source and the coupler units. When the twist angle is very large, the nature of intramolecular magnetic interaction changes from ferromagnetic to antiferromagnetic. In these cases, the coupler-NN bond order becomes small. Substitution at the common meta position of m-phenylene in the diradical has little steric and hydrogen-bonding effects. Electron-withdrawing groups reveal a specific trend for single-atom substitution. An ortho substitution generally decreases J and a meta substitution always increases J with a decreasing -I effect. Variation of J with planarity as well as Hammett constant is investigated. The nucleus-independent chemical shift value is found to decrease from the corresponding mono-substituted phenyl derivatives. The dependence of J on these factors is explored

The structural relaxation of the alpha-Al2O3(0001) - an investigation of potential errors

Consider a lossy packet network of queues, communicating over a wireless medium. This paper presents a throughput-optimal transmission strategy for a unicast network when feedback is available, which has the following advantages: It requires a very limited form of acknowledgment feedback. It is completely distributed, and independent of the network topology. Finally, communication at the information theoretic cut-set rate requires no network coding and no rateless coding on the packets. This simple strategy consists of each node randomly choosing a packet from its buffer to transmit at each opportunity. However, the packet is only deleted from a node's buffer once it has been successfully received by the final destinatio