Performance of density functional theory in computing nonresonant vibrational (hyper)polarizabilities

A set of exchange‐correlation functionals, including BLYP, PBE0, B3LYP, BHandHLYP, CAM‐B3LYP, LC‐BLYP, and HSE, has been used to determine static and dynamic nonresonant (nuclear relaxation) vibrational (hyper)polarizabilities for a series of all‐trans polymethineimine (PMI) oligomers containing up to eight monomer units. These functionals are assessed against reference values obtained using the Møller–Plesset second‐order perturbation theory (MP2) and CCSD methods. For the smallest oligomer, CCSD(T) calculations confirm the choice of MP2 and CCSD as appropriate for assessing the density functionals. By and large, CAM‐B3LYP is the most successful, because it is best for the nuclear relaxation contribution to the static linear polarizability, intensity‐dependent refractive index second hyperpolarizability, static second hyperpolarizability, and is close to the best for the electro‐optical Pockels effect first hyperpolarizability. However, none of the functionals perform satisfactorily for all the vibrational (hyper)polarizabilities studied. In fact, in the case of electric field‐induced second harmonic generation all of them, as well as the Hartree–Fock approximation, yield the wrong sign. We have also found that the Pople 6–31+G(d) basis set is unreliable for computing nuclear relaxation (hyper)polarizabilities of PMI oligomers due to the spurious prediction of a nonplanar equilibrium geometry. © 2013 Wiley Periodicals, Inc.     

Catalytic Reduction of Oximes to Hydroxylamines: Current Methods,Challenges and Opportunities

Catalytic reduction of oximes represents a direct efficient approach to synthesize valuable hydroxylamine derivatives. However this transformation presents significant challenges: oximes are hard to reduce and, if reactive, reductive cleavage of the weak N−O bond often leads to primary amine side products. The first suitable systems involved the use of platinum-based heterogeneous catalysts with hydrogen as reductant and stoichiometric amounts of a strong Brønsted acid. More recently metal-free and transition-metal-based homogeneous catalysts have been developed, which display the highest turnovers (up to 4000). In the asymmetric variants, the E/Z-geometry of the oxime double bond affects significantly the stereoselectivity, sometimes requiring extra synthetic efforts in substrate preparation. This minireview provides an overview of the advances and limitations in catalytic oxime to hydroxylamine reduction. Emphasis is put on highlighting and comparing the practical aspects of the existing methods, such as their reaction conditions and substrate scope. Additionally, future directions for improving this young research area are suggested.     

An axiomatic characterization of the potential decisiveness index

Let us consider that somebody is extremely interested in increasing the probability of a proposal to be approved by a certain committee and that to achieve this goal he/she is prepared to pay off one member of the committee. In a situation like this one, and assuming that vote-buying is allowed and free of stigma, which voter should be offered a bribe? The potential decisiveness index for simple games, which measures the effect that ensuring one positive vote produces for the probability of passing the issue at hand, is a good tool with which to acquire the answer. An axiomatic characterization of this index is given in this paper, and its relation to other classical power indices is shown.     

Locating saddle points of any index on potential energy surfaces by the generalized gentlest ascent dynamics

The system of ordinary differential equations for the method of the gentlest ascent dynamics (GAD) is tested to determine the saddle points of the potential energy surface of some molecules. The method has been proposed earlier [E and Zhou in Nonlinearity 24:1831 (2011)]. We additionally use the metric of curvilinear internal coordinates. By a number of examples, we explain the possibilities of a GAD curve; it can find the transition state of interest by a gentlest ascent, directly or indirectly, or not. A GAD curve can be a model of a reaction path, if it does not contain a turning point for the energy. We further discuss generalized GAD formulas for the search of saddle points of a higher index. We calculate diverse examples.     

Aryl‐Copper(III)‐Acetylides as Key Intermediates in CCsp Model Couplings under Mild Conditions

The mechanism of copper‐mediated Sonogashira couplings (so‐called Stephens–Castro and Miura couplings) is not well understood and lacks clear comprehension. In this work, the reactivity of a well‐defined aryl‐Cu^III species ( 1 ) with p‐R‐phenylacetylenes (R=NO₂, CF₃, H) is reported and it is found that facile reductive elimination from a putative aryl‐Cu^III‐acetylide species occurs at room temperature to afford the C_aryl?C_sp coupling species ( I_R ), which in turn undergo an intramolecular reorganisation to afford final heterocyclic products containing 2H‐isoindole ( P , P , P_Ha ) or 1,2‐dihydroisoquinoline ( P_Hb ) substructures. Density Functional Theory (DFT) studies support the postulated reductive elimination pathway that leads to the formation of C?C_sp bonds and provide the clue to understand the divergent intramolecular reorganisation when p‐H‐phenylacetylene is used. Mechanistic insights and the very mild experimental conditions to effect C_aryl?C_sp coupling in these model systems provide important insights for developing milder copper‐catalysed C_aryl?C_sp coupling reactions with standard substrates in the future.     

Interfacial Chiral Selection by Bulk Species

A chiral selection process in a self‐assembled soft monolayer of an achiral amphiphile as a consequence of its interaction with chiral species dissolved in the aqueous subphase, is reported. The extent of the chiral selection is statistically measured in terms of the enantiomorphic excess of self‐assembled submillimeter domains endowed with well‐defined orientational chirality that is unambiguously resolved using optical microscopy. Our results show that the emergence of chirality is mediated by electrostatic interactions and significantly enhanced by hydrophobic effects. This chiral chemical effect can be suppressed and even reversed by opposing a macroscopic physical influence, such as vortical stirring. This result gives evidence for the crucial role of hydrodynamic effects in supramolecular aggregation.     

Synthesis of Enantiomeric Pure E-Nor-15-azayohimbines

A stereodivergent synthesis of enantiomerically pure E-nor-15-azayohimbines via condensation of tryptamine with derivatives of pyroglutamate 4 is reported. When the Pictet-Spengler reaction was induced in refluxing aqueous AcOH a nearly equimolar ratio of lactams 7 and 8 was obtained, whereas under kinetic control (TFA, room temperature) the trans-derivative 8 was the major product. In contrast, cyclization of amido acetal 12 with TsOH gave the cis-derivative 7 as preponderant component.     

Origin of the asymmetric magnetization reversal behavior in exchange-biased systems: competing anisotropies

The magnetization reversal in exchange-biased ferromagnetic-antiferromagnetic (FM-AFM) bilayers is investigated. Different reversal pathways on each branch of the hysteresis loop, i.e., asymmetry, are obtained both experimentally and theoretically when the magnetic field is applied at certain angles from the anisotropy direction. The range of angles and the magnitude of this asymmetry are determined by the ratio between the FM anisotropy and the interfacial FM-AFM exchange anisotropy. The occurrence of asymmetry is linked with the appearance of irreversibility, i.e., finite coercivity, as well as with the maximum of exchange bias, increasing for larger anisotropy ratios. Our results indicate that asymmetric hysteresis loops are intrinsic to exchange-biased systems and the competition between anisotropies determines the asymmetric behavior of the magnetization reversal.     

Classification of Dansgaard–Oeschger climatic cycles by the application of similitude signal processing

In this work we have performed a detailed analysis, using signal processing tools, to study time series of data (temperature proxy) extracted from the GRIP ice-core records and we relate it with the evolution of atmospheric CO₂ within the last glacial period. Our method is based in considering the warm periods known as Dansgaard–Oeschger (D/O) events and posterior returns to the cold stage as a climatic cycle. After the warming phase, D/O events relax to the initial cold state in three different ways, what gives rise to three classes of cycles. Also, the Younger/Dryas–Bolling/Allerod (Y/D–B/A) cycle corresponds to one of the classes obtained. We have found that all cycles start with identical warming phases which seem completely unrelated to variations in CO₂ concentration. We discuss on the consequences for global climatology of such steady pattern of cycles.