The Hund paradox and stabilization of molecular chiral states

The “paradox of optical isomers” revealed by Hund in 1927 is re-examined taking into account the interaction of a chiral molecule with phonons of optically inactive solids below the Debye temperature θ_D. It has been shown, that in the strong coupling limit, where the dephasing rate is much higher than the energy splitting frequency, the interaction can lead to a complete loss of coherence between mirror-antipodal states of the molecule due to the phonon-induced dephasing. This, in turn, suppresses tunnelling oscillations between them, so that transitions, which are reversible in time for an isolated chiral molecule become irreversible for the same molecule placed in a low-temperature matrix. In order to propose a particular mechanism of such stabilization, contributions of a single- and multi-phonon processes in the dephasing rate have been evaluated. It has been established that only the two-phonon scattering provides the sufficiently strong dephasing in low-temperature solids. Such a two-phonon mechanism is responsible for the stabilization of molecular chiral states as long as the temperature of the medium is lower θ_D, but exceeds a few Kelvin degrees. These findings are discussed in the context of the evolutionary concept known as “the cold prehistory of life”.     

On the Reactivity and Stability of Iodide–Nitride–Sulfide Clusters of Neodymium and Dysprosium

The thermal decomposition of cluster Nd₃I₅(S₂)(S₂N₂)(THF)10 (I) at 50–400°C affords a mixture of products among which tetrahydrofuran (THF), sulfur, diiodine, HI, H₂S, CS₂, S₃N₆, S₃N₅, MeI, thiophene, tetrahydrothiophene, diiodobutane, iodobutene, and NdI₃ are identified. The treatment of Ln₃I₅(S₂)(S₂N₂)(THF)₁₀ (Ln = Nd (I), Dy (II)) with phenanthroline (Phen) in THF at room temperature results in the partial substitution of ТНF to form new complexes Ln₃I₅(S₂)(S₂N₂)(THF)₄(Phen)₃. The dissolution of compound I in pyridine gives a pyridine (Py) complex Ln₃I₅(S₂)(S₂N₂)(THF)3(Py)₇. The dissolution of compounds I and II in acetonitrile at 20°C is accompanied by the fast rearrangement and fragmentation of the complexes to form LnI₃(MeCN)₆, [LnI(S₂)(MeCN)], and [LnI(S₂N₂)(MeCN)]. Complex I in THF does not react with white phosphorus, carbon monoxide, fullerene C₆₀, and chromium hexacarbonyl.     

Absorption-induced confinement of lasing modes in diffusive random media

We present a numerical study of lasing modes in diffusive random media with local pumping. The reabsorption of emitted light suppresses the feedback from the unpumped part of the sample and effectively reduces the system size. The lasing modes are dramatically different from the quasi modes of the passive system (without gain or absorption). Even if all the quasi modes of a passive diffusive system are extended across the entire sample, the lasing modes are still confined in the pumped volume with an exponential tail outside it. The reduction of effective system volume by absorption broadens the distribution of decay rates of quasi modes and facilitates the occurrence of discrete lasing peaks.     

Numerical study of light correlations in a random medium close to the Anderson localization threshold

We applied a finite-difference time domain algorithm to the study of field and intensity correlations in random media. Close to the onset of Anderson localization, we observe deviations of the correlation functions, in both shape and magnitude, from those predicted by the diffusion theory. Physical implications of the observed phenomena are discussed.     

Reduction of the groups C=O and C=N with neodymium and dysprosium diiodide hydrides

Neodymium diiodide hydride under mild conditions adds at the carbonyl group of benzophenone to give (diphenylmethoxy)(diiodo)neodymium(iii) of the formula I₂Nd(OCHPh₂)(THF)₄. In reactions of NdI₂H and DyI₂H with N-(2,6-diisopropylphenyl)-9,10-phenanthrenequinonimine, the system of conjugated C=N and C=O groups of the quinone is reduced. The resulting o-aminophenanthrolate complexes are structurally characterized by X-ray diffraction.     

Phantom expansion with non-linear Schrödinger-type formulation of scalar field cosmology

We describe non-flat standard Friedmann cosmology of canonical scalar field with barotropic fluid in form of non-linear Schrödinger-type (NLS) formulation in which all cosmological dynamical quantities are expressed in term of Schrödinger quantities as similar to those in time-independent quantum mechanics. We assume the expansion to be superfast, i.e. phantom expansion. We report all Schrödinger-analogous quantities to scalar field cosmology. Effective equation of state coefficient is analyzed and illustrated. We show that in a non-flat universe, there is no fixed w _eff value for the phantom divide. In a non-flat universe, even w _eff > ?1, the expansion can be phantom. Moreover, in open universe, phantom expansion can happen even with w _eff > 0. We also report scalar field exact solutions within frameworks of the Friedmann formulation and the NLS formulation in non-flat universe cases.     

Relaxation in glasses at low temperatures

JETP Letters - The interaction between tunneling system inherent in amorphous solids is established to be responsible for the universal behavior of their kinetics and thermodynamic properties at...     

Effect of nuclear quadrupole interactions on the dynamics of two-level systems in glasses

The standard tunneling model describes quite satisfactorily the properties of amorphous solids at temperatures T < 1K in terms of an ensemble of two-level systems including the logarithmic temperature dependence of the dielectric constant. Yet, experiments have shown that at ultralow temperatures T< 5 mK such a temperature behavior breaks down and the dielectric constant becomes temperature independent (plateau effect). In this Letter we suggest an explanation of this behavior exploiting the effect of the nuclear quadrupole interaction on tunneling. We also predict that the application of a sufficiently large magnetic field B> 10T should restore the logarithmic dependence because of the suppression of the nuclear quadrupole interaction.