On the local mode behaviour of the XH2/XD2 and XD/XH fragments with respect to the deuterated species of the near local mode XH3(C3v ) molecule

Effect of isotopic substitution in the near local mode, XH₃(C_3v ), molecules is considered. On that basis it is shown that the spectroscopic properties of deuterated and/or di-deuterated isotopic species of the XH₃(C_3v ) molecule with the value of interbond angle close to π/2 are analogous to the spectroscopic properties of its separate fragments: of a three-atomic local mode ‘molecule’ XH₂/XD₂ and of a diatomic XD/XH ‘molecule’. The phosphine molecule is considered as an illustration.     

Berechnung der Amplitudenfluktuation eines mit Laserlicht gepumpten optischen parametrischen Oszillators

The intensity fluctuations of the radiation of an optical parametric oscillator have been calculated by taking into account the corresponding fluctuations of the pump light. The latter are shown to have a strong influence on the fluctuations of signal and idler waves. In contrary to the laser case, they are essentially reproduced in the signal and idler radiation; more quantitatively, the correlation function 〈?(t₁) ?(t₂)〉 where ? denotes the deviation of the amplitude of the signal (or idler) wave from its mean value is, for t₁ = t₂, equal to the corresponding quantity for the pump wave apart from a reduction factor, whose value depends on the resonator losses and the relative excitation of both the pumping laser and the optical parametric oscillator and is found to be of the order of one for the normal case. It is interesting to note that for sufficiently strong pumping, the correlation function 〈?(t₁) ?(t₂)〉 approaches the value zero for |t₁ – t₂| → ∞ not monotonically but in form of damped oscillations.     

The temperature dependence of rotational tunneling

In the last few years tunneling transitions have been observed for the highly symmetric groups CH₄, CD₄, NH ₄ ⁺ , and CH₃ rotating in various environments. Typically the tunneling lines shift to lower energies with increasing temperatures. In this paper the shift of the tunneling energy is calculated in a microscopic approach to the problem. The coupling of the rotating groups to the lattice modes is studied in two stages. First the rotating group is coupled to a single oscillator, then to the modes of a Debye crystal. The first calculation leads to a set of discrete tunneling lines with an energy that diminishes as the oscillator is excited into higher levels. The second approach yields a single tunneling line shifted down-wards with increasing phonon population. The shift is proportional toT ⁴. The calculation explains the energy shift of the tunneling lines with reasonable values for the coupling parameters. In some cases also a broadening has been observed which does not follow from our calculations.     

Thermodynamic,kinetic, and mechanistic examination of 1,5‐ dihydro‐3,4‐dihydroxy‐2‐pyrrolone derivatives as a new type of antioxidants to mimic vitamin C

In this work, 1,5‐dihydro‐3,4‐dihydroxy‐2‐pyrrolone derivatives (XH₂) and their anions (XH^?) were designed and synthesized as the synthetic vitamin C analogs. The thermodynamic driving forces of the 8 possible elementary steps for XH₂ to release 2 hydrogen atoms to become X in acetonitrile were determined using experimental methods. The mechanisms and the possible reaction intermediates of XH₂ and XH^? reacted by DPPH ^? in acetonitrile were examined or predicted using the determined thermodynamic analysis combining the kinetics.     

Calculating thermopower due to fluctuation-assisted tunnelling with application to carbon nanotube ropes

We show how Sheng's theory of fluctuation-assisted tunnelling can be used to calculate thermopower due to the presence of quantum mechanical tunnelling barriers. For a hole-like situation, this calculated thermopower behaviour increases approximately linearly with increasing temperature (commencing from zero in the zero temperature limit) until a knee is reached, after which the thermopower continues to increase linearly but with a reduced slope. In Sheng's theory, the amplitude for the barrier fluctuations increases with increasing temperature and the knee occurs when the thermal fluctuations become comparable to the magnitude of the tunnelling barriers. Interestingly, this thermopower behaviour compares quite favourably with that measured for systems of metallic single-walled carbon nanotubes (SWCNs) and, in particular, the knee seen in the temperature dependence of the carbon nanotube thermopower data at T∼100 K arises naturally in our calculation. For a system of carbon nanotubes, tunnelling barriers could occur either between individual carbon nanotubes or else due to defects within the carbon nanotubes.     

Defect induced fluctuations in the paraelectric phase of KTa0.94Nb0.06O3

First order Raman lines observed in the paraelectric phase of KTa_0.94Nb_0.06O₃ are shown to be the result of odd symmetry microdistortions or fluctuations with a correlation length that extends to several unit cells. The possibilities that the lines result from impurity induced or disorder induced Raman scattering are considered and discarded. From simple theoretical considerations it is shown that the integrated intensity of distortion induced first order Raman lines, normalized by the corresponding phonon occupation numbers, is proportional to the average distortion intensity. This proportionality is independent of the correlation length of the distortion field provided it is larger than a certain minimum.Using this relation and the experimentally measured integrated intensity of the TO₂ line we find that the average distortion intensity is proportional toT/(T _c—T). This result is compared to two models which qualitatively predict the existence of microdistortions or fluctuations in the paraelectric phase. The experimentally observed temperature dependence is found to be consistent with the defect induced fluctuations model and inconsistent with continuous phase transitions models.     

Quantum correlations and fluctuations in the pulsed light produced by a synchronously pumped optical parametric oscillator below its oscillation threshold

We present a simple quantum theory for the pulsed light generated by a synchronously pumped optical parametric oscillator (SPOPO) in the degenerate case where the signal and idler trains of pulses coincide, below threshold and neglecting all dispersion effects. Our main goal is to precise in the obtained quantum effects, which ones are identical to the c.w. case and which ones are specific to the SPOPO. We demonstrate in particular that the temporal correlations have interesting peculiarities: the quantum fluctuations at different times within the same pulse turn out to be totally not correlated, whereas they are correlated between nearby pulses at times that are placed in the same position relative to the center of the pulses. The number of significantly correlated pulses is of the order of cavity finesse. We show also that there is perfect squeezing at noise frequencies W_m\Omega_m = 2π m/T _R (m = 0, 1, 2,?\ldots where T _R is the pulse train period) when one approaches the threshold from below on the signal field quadrature measured by a balanced homodyne detection with a local oscillator of very short duration compared to the SPOPO pulse length.     

Understanding the reaction between muonium atoms and hydrogen molecules: zero point energy,tunnelling, and vibrational adiabaticity

The advent of very precise measurements of rate coefficients in reactions of muonium (Mu), the lightest hydrogen isotope, with H₂ in its ground and first vibrational state and of kinetic isotope effects with respect to heavier isotopes has triggered a renewed interests in the field of muonic chemistry. The aim of the present article is to review the most recent results about the dynamics and mechanism of the reaction Mu+H₂ to shed light on the importance of quantum effects such as tunnelling, the preservation of the zero point energy, and the vibrational adiabaticity. In addition to accurate quantum mechanical (QM) calculations, quasiclassical trajectories (QCT) have been run in order to check the reliability of this method for this isotopic variant. It has been found that the reaction with H₂(v=0) is dominated by the high zero point energy (ZPE) of the products and that tunnelling is largely irrelevant. Accordingly, both QCT calculations that preserve the products’ ZPE as well as those based on the Ring Polymer Molecular Dynamics methodology can reproduce the QM rate coefficients. However, when the hydrogen molecule is vibrationally excited, QCT calculations fail completely in the prediction of the huge vibrational enhancement of the reactivity. This failure is attributed to tunnelling, which plays a decisive role breaking the vibrational adiabaticity when v=1. By means of the analysis of the results, it can be concluded that the tunnelling takes place through the ν₁=1 collinear barrier. Somehow, the tunnelling that is missing in the Mu+H₂(v=0) reaction is found in Mu+H₂(v=1).     

Variational transition state theory with multidimensional tunnelling and kinetic isotope effects in the reactions of C2H6, C2H5D and C2D6 with .CCl3 to produce CHCl3 and CDCl3

ABSTRACT

Rate constants for the reactions of C₂H₆, C₂H₅D and C₂D₆ with .CCl₃. for the production of CHCl₃ and CDCl₃ (k₁, k₂, k₃ and k₄) were computed using variational transition state theory coupled with hybrid-meta density functional theory (MPWB1K) over the temperature range of 200–2900 K. The ground-state vibrational adiabatic potential was plotted for all channels. Small- and large-curvature tunnelling were determined to include quantum effects in the calculation of rate constants. Harmonic vibrational frequencies along the reaction path were calculated in curvilinear coordinates with scaled frequencies. Anharmonicity was included in the lowest-frequency torsion. The position of formation and dissociation of bonds was specified using the variation in harmonic vibrational frequencies along the reaction path. Representative tunnelling energy and the thermally averaged transmission probability at 298 K (P(E)exp?( ? ΔE/RT)) were determined for the reactions in which tunnelling is important. The kinetic isotope effect was used to calculate the considerable contributions of tunnelling and vibration. The expressions for rate constants were determined using nonlinear least-square fitting over the temperature range of 200–2900 K.     

Effect of free electron-hole pairs on the saturation of excitonic absorption in GaAs/AlGaAs quantum wells

The pump-probe experimental method is used to investigate the effect of photoexcited carriers on the dynamics of the exciton absorption spectra of GaAs / Al_xGa_1–x As-multilayer quantum wells. Use of the method of moment analysis for processing the results makes it possible to identify the simultaneous contribution of changes in oscillator strength and width of the exciton lines in the saturation of exciton absorption. It was found that the oscillator strength recovers its initial value in the course of the first 100–130 ps, whereas broadening and energy-shift of the exciton lines is observed for 700–800 ps. These are the first experimental measurements of the excitation densities at which the oscillator strength of the excitonic state saturates when the latter is perturbed only by free-electron-hole pairs, and when it is perturbed only by other excitons. Fiz. Tverd. Tela (St. Petersburg) 40, 1130–1133 (June 1998)     

Dynamics of excitonic states in GaAs/AlGaAs quantum wells

The influence of photoexcited carriers on the dynamics of the absorption spectra of GaAs/Al_xGa_1−2x As multilayer quantum wells is investigated experimentally. It is found that at quasiparticle densities all the way up to 10¹¹ cm⁻² the saturation of the excitonic absorption is due to both a decrease of oscillator strength and broadening of the excitonic lines. It is shown that in the case of femtosecond resonance laser exci-tation the decrease of oscillator strength is due to free electron-hole pairs, while the broadening and energy shift of the excitonic lines are due to the exciton-exciton interaction. The lifetimes of free electron-hole pairs and excitons (≈65 ps and ≈410 ps, respectively) are determined from the exponential decrease of the change in the oscillator strength and in the width and energy position of the excitonic lines. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 3, 139–144 (10 August 1997)     

Rotation-vibration energy cluster formation in XH2D and XHD2 molecules (X = Bi, P, and Sb)

We investigate theoretically the energy cluster formation in highly excited rotational states of several pyramidal XH₂D and XHD₂ molecules (X = Bi, P, and Sb) by calculating, in a variational approach, the rotational energy levels in the vibrational ground states of these species for J?70. We show that at high J the calculated energy levels of the di-deuterated species XHD₂ exhibit distinct fourfold cluster patterns highly similar to those observed for H₂X molecules. We conclude from eigenfunction analysis that in the energy cluster states, the XHD₂ molecule rotates about a so-called localization axis which is approximately parallel to one of the X-D bonds. For the mono-deuterated XH₂D isotopologues, the rotational spectra are found to have a simple rigid-rotor structure with twofold clusters.     

Radiation damping in an anharmonic oscillator

The effect of radiation damping in an anharmonic oscillator has been calculated using the technique of Kryloff and Bogolituboff. It is found that the intensity distribution of the emitted spectral line is asymmetric about its intensity maximum. The index of asymmetry agree with the experimental data on x-rayK _{a 1,2}lines.     

Sensitivity- and Gradient-Enhanced Hetero (ω1) Half-Filtered TOCSY Experiment for Measuring Long-Range Heteronuclear Coupling Constants

An enhanced version of the X(ω₁) half-filtered TOCSY experiment for measurement of long-range heteronuclear coupling constants is proposed which yields high-quality spectra with substantially increased sensitivity and resolution. The modified method features gradient-enhanced X filtering sequences, broadband homonuclear decoupling duringt₁, optional¹J_XHscaling in theF₁domain, and gradient coherence selection in combination with the sensitivity-enhanced protocol for the TOCSY transfer. These modifications extend the applicability of the method—coupling constants can be measured accurately for natural abundance samples at low concentrations and for compounds yielding complex spectra. Computer-aided analysis of E.COSY-type multiplets is applied for the determination of heteronuclear long-range coupling constants.     

Barrier parameters and superconducting gap structure of the etched surface of Y−Ba−Cu−O by scanning tunnelling spectroscopy

Summary Using a scanning tunnelling microscope, the tunnelling currentvs. voltage is measured between a gold tip and the chemically etched (001) surface of YBa₂Cu₃O _x crystals at room temperature. The tunnelling barrier height and thickness are derived by modelling the system in the normal state as a conventional N-I-N junction. TheI(V) andG(V) curves are computed for the same junction in the superconducting state (N-I-S junction). The predicted gap structure for a single BCS-Dynes-like gap is simple and has low zero-bias conductance. The complexG(V) spectra measured belowT _c on the etched junctions with ∼ 50% zero-bias conductance suggest a possible multilayer contribution in the unit cell. In honour of Prof. Fausto Fumi on the occasion of his retirement from teaching.     

Multiband calculation of exciton diamagnetic shift in InP/InGaP self-assembled quantum dots

Exciton states in self-assembled InP/In_0.49Ga_0.51P quantum dots subject to magnetic fields up to 50 T are calculated. Strain and band mixing are explicitly taken into account in the single-particle models of the electronic structure, while an exact diagonalization approach is adopted to compute the exciton states. Reasonably good agreement with magneto-photoluminescence measurements on InP self-assembled quantum dots is found. As a result of the polarization and angular momentum sensitive selection rules, the exciton ground state is dark. For in-plane polarized light, the magnetic field barely affects the exciton spatial localization, and consequently the exciton oscillator strength for recombination increases only slightly with increasing field. For z polarized light, a sharp increase of the oscillator strength beyond 30 T is found which is attributed to the enhanced s character of the relevant portion of the exciton wave function.     

The polarization dependence of the multipole absorption probability and the optical activity of racemic mixtures

The dynamics of concentration fluctuations of polystyrene ([Mbar] _w = 20 000) in cyclohexane are studied as a function of temperature and concentration using the photon correlation spectroscopic technique. Over a 60°C temperature range, the translational diffusion coefficient [Dbar] _c changes by more than two orders of magnitude. At a given temperature, [Dbar] _c first decreases with increasing concentration until a critical concentration C* at 22 per cent is reached, beyond which [Dbar] _c increases with increasing concentration, reaching a maximum at higher concentration. The critical concentration C* is insensitive to temperature variations and cannot be identified with the overlap concentration of the entangled polymer. The scattering intensity as a function of concentration also shows a maximum at C*, suggesting that the slowing down of concentration fluctuations due to the decrease in (?μ/?C) _P,T is responsible for the intensity maximum. It is concluded that the emergence of the cooperative motion at C* is closely related to the effects of critical phenomena observed at the cloud point.     

Tunneling conductance in quantum wire/insulator/dx2 -y2 + idxy mixed wave superconductor junctions

Using the extended Blonder-Tinkham-Klapwijk (BTK) theory, this paper calculates the tunnelling conductance in quantum wire/insulator/dx2-y2 + idxy mixed wave superconductor (q/I/dx2-y2 + idxy) junctions. That is different from the case in d- and p-wave superconductor junctions. When the angle α between a-axis of the dx2-y2 wave superconductor and the interface normal is π/4, there follows a rather distinctive tunnelling conductance. The zero-bias conductance peak (ZBCP) may or may not appear in the tunnelling conductance. Both the interface potential z and the quasi-particle lifetime factor Γ are smaller, there is no ZBCP. Otherwise, the ZBCP will appear. The position of bias conductance peak (BCP) depends strongly on the amplitude ratio of two components for dx2-y2 + idxy mixed wave. The low and narrow ZBCP may coexist with the BCP in the tunnelling conductance. Using those features in the tunnelling conductance of q/I/dx2-y2 + idxy junctions, it can distinguish dx2-y2 + idxy mixed wave superconductor from d- and p-wave one.     

Sensitivity- and Gradient-Enhanced Hetero (ω1) Half-Filtered TOCSY Experiment for Measuring Long-Range Heteronuclear Coupling Constants

An enhanced version of the X(ω₁) half-filtered TOCSY experiment for measurement of long-range heteronuclear coupling constants is proposed which yields high-quality spectra with substantially increased sensitivity and resolution. The modified method features gradient-enhanced X filtering sequences, broadband homonuclear decoupling duringt₁, optional¹J_XHscaling in theF₁domain, and gradient coherence selection in combination with the sensitivity-enhanced protocol for the TOCSY transfer. These modifications extend the applicability of the method—coupling constants can be measured accurately for natural abundance samples at low concentrations and for compounds yielding complex spectra. Computer-aided analysis of E.COSY-type multiplets is applied for the determination of heteronuclear long-range coupling constants.     

A finite fractal cluster theory of 1/f noise in percolation systems near metal-insulator transition

The problem of 1/f noise in thin metal films and metal-insulator composites in the scaling fractal regime near percolation threshold is considered. The correspondence between a percolation transition and a second order phase transition is extended from the point of view of electronic polarization and electrical fluctuations. The charge fluctuations on finite fractal clusters are argued to be analogous to spontaneous order parameter fluctuations in phase transitions, being correlated upto percolation correlation length. The charge relaxation times are shown to be related to the cluster sizes having distribution function of the formg()^–b , whereb is connected to Euclidean and fractal dimensionalities and critical exponents. This produces the 1/f noise spectrum. Below percolation threshold, the nodes-links-blobs picture is invoked such that the blobs represent metallic conductances of the finite clusters and the links are tunnelling conductances between them through narrowest barrier regions. Above threshold, the finite cluster network is visualized as connected to the infinite cluster through narrowest tunnelling regions. The correlated spontaneous charge fluctuation on finite fractal clusters is held responsible for conductance fluctuation on either side of the metal-insulator transition via tunnelling processes. Finally, the scaling behaviour of noise magnitude near percolation threshold is explained.