A Perspective on Designing Chiral Organic Magnetic Molecules with Unusual Behavior in Magnetic Exchange Coupling.

A total of nine diradical-based organic chiral magnetic molecules with allene and cumulene couplers have been theoretically designed, and subsequently, their magnetic property has been studied by density functional theory. It is found that with an increase in length of the coupler, a remarkable increase in spin density within the coupler takes place. An increase in the length of the coupler reduces the energy of LUMO, and a smaller HOMO-LUMO gap facilitates stronger magnetic coupling and thereby a higher magnetic exchange coupling constant (J).

Clar theory extended for polyacenes and beyond.

An extension of Clar's classical sextet ideas is presented to allow resonance-based weak-pairing long bonds. As the prototypic illustration, the theory is developed in the context of polyacenes, where this extension is needed to properly understand what goes on in this sort of polymer, whose radicality increases with chain length. A quantification of these novel Clar-sextic ideas is made, and detailed computational results are reported for the polyacenes even to the limit of arbitrary long chains.

A theoretical study on photomagnetic fluorescent protein chromophore coupled diradicals and their possible applications.

We have designed and theoretically studied three different pairs of green fluorescent protein chromophores and their different homologue-based diradicals coupled with imino nitroxides. To begin with, the geometries of all these diradicals have been optimized at high spin (HS) state in the gas phase, in a water medium and in a blood plasma medium. The process of calculations is straightforward and well-established in the case of the gas phase.

A DFT study on the magnetostructural property of ferromagnetic heteroverdazyl diradicals with phenylene coupler.

We have theoretically designed five different m-phenylene coupled high-spin bis-heteroverdazyl diradicals and their analogous p-phenylene coupled low-spin positional isomers. The geometry-based aromaticity index, harmonic oscillator model of aromaticity (HOMA) values for both the couplers (local HOMA), and the whole diradicals (global HOMA) have been calculated for all the diradicals. We also qualitatively relate these HOMA values with the intramolecular magnetic exchange coupling constants (J), calculated using a broken symmetry approach within unrestricted density functional theory framework.

Unusually large coupling constants in diradicals obtained from excitation of mixed radical centers: a theoretical study on potential photomagnets.

Three sets of heterosubstituted, interconvertible, cyclophanediene (CPD), and dihydropyrenes (DDPs) and one such set involving dinitrilepyrenes were examined by UB3LYP broken-symmetry methodology with 6-311++g(d,p) bases. Nitronyl nitroxide and oxoverdazyl (with both N and C terminals) are monoradical centers, whereas CPD and DDP moieties serve as couplers. The photoexcited CPD converts to DDP.

Very strongly ferromagnetically coupled diradicals from mixed radical centers. II. Nitronyl nitroxide coupled to tetrathiafulvalene via spacers.

We predict large and positive intramolecular magnetic exchange coupling constants (J) for coupled diradicals constructed from nitronyl nitroxide and tetrathiafulvalene monoradical moieties. These diradicals have the general formula TTF-coupler-NN, where the couplers are mostly aromatic systems. Unrestricted density functional methodology (UB3LYP) has been used to optimize the molecular geometries of the triplet diradicals using the 6-311 g(d,p) basis set.

All-temperature magnon theory of ferromagnetism.

We present an all-temperature magnon formalism for ferromagnetic solids. To our knowledge, this is the first time that all-temperature spin statistics have been calculated. The general impression up to now is that the magnon formalism breaks down at the Curie point as it introduces a series expansion and unphysical states.

Very strongly ferromagnetically coupled diradicals from mixed radical centers: nitronyl nitroxide coupled to oxoverdazyl via polyene spacers.

We predict extremely large and positive intramolecular magnetic exchange coupling constants (J) for coupled diradicals constructed from nitronyl nitroxide (NN) and oxoverdazyl (o-VER). These radicals have the general formula o-VER(N)-nC-NN where nC represents an olefinic spacer with n = 0, 2, 4, 6, and 8. Species like o-VER(C)-nC-NN have negative coupling constants.

Unique rate expression for glucose production in C(4) plants.

A physicochemical interpretation of a recently formulated temperature-dependent, steady-state rate expression for the production of glucose equivalent in C(4) plants is given here. We show that the rate equation is applicable to a wide range of C(4) plants.

Integrated kinetics for the production of glucose in plant cells and the effect of temperature.

We prepare a temperature-dependent formulation of the integrated kinetics for the overall process of photosynthesis in eukaryotic cells. To avoid complexity, the C4 plants are chosen because their rate of photosynthesis is independent of the partial pressure of O2. A systematically simplified but comprehensive scheme for both light and dark reactions is considered.