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61.
Sharmistha Karmakar Dr. Ayan Datta 《Angewandte Chemie (International ed. in English)》2014,53(36):9587-9591
At room temperature, 1,2‐hydrogen‐transfer reactions of N‐heterocyclic carbenes, like the imidazol‐2‐ylidene to give imidazole is shown to occurr almost entirely (>90 %) by quantum mechanical tunneling (QMT). At 60 K in an Ar matrix, for the 2, 3‐dihydrothiazol‐2‐ylidene→thiazole transformation, QMT is shown to increase the rate about 105 times. Calculations including small‐curvature tunneling show that the barrier for intermolecular 1,2‐hydrogen‐transfer reaction is small, and QMT leads to a reduced rate of the forward reaction because of nonclassical reflections even at room temperature. A small barrier also leads to smaller kinetic isotope effects because of efficient QMT by both H and D. QMT does not always lead to faster reactions or larger KIE values, particularly when the barrier is small. 相似文献
62.
Two Ru(II) complexes, [Ru(bpy)2L](ClO4)2 (1) and [Ru(bpy)2L'](BF4)2 (2), where bpy is 2,2'-bipyridine, L is diacetyl dihydrazone, and L' 1:2 is the condensate of L and acetone, are synthesized. From X-ray crystal structures, both are found to contain distorted octahedral RuN(6)(2+) cores. NMR spectra show that the cations in 1 and 2 possess a C2 axis in solution. They display the expected metal-to-ligand charge transfer (1MLCT) band in the 400-500 nm region. Complex 1 is nonemissive at room temperature in solution as well as at 80 K. In contrast, complex 2 gives rise to an appreciable emission upon excitation at 440 nm. The room-temperature emission is centered at 730 nm (lambda(em)(max)) with a quantum yield (Phi(em)) of 0.002 and a lifetime (tau(em)) of 42 ns in an air-equilibrated methanol-ethanol solution. At 80 K, Phi(em) = 0.007 and tau(em) = 178 ns, with a lambda(em)(max) of 690 nm, which is close to the 0-0 transition, indicating an 3MLCT excited-state energy of 1.80 eV. The radiative rate constant (5 x 10(4) s(-1)) at room temperature and 80 K is almost temperature independent. From spectroelectrochemistry, it is found that bpy is easiest to reduce in 2 and that L is easiest in 1. The implications of this are that in 2 the lowest (3)MLCT state is localized on a bpy ligand and in 1 it is localized on L. Transient absorption results also support these assignments. As a consequence, even though 2 shows a fairly strong and long-lived emission from a Ru(II) --> bpy CT state, the Ru(II) --> L CT state in 1 shows no detectable emission even at 80 K. 相似文献
63.
Optical and static dielectric studies on a terminally fluorinated liquid crystalline compound have been carried out. Measurements of temperature variation of refractive indices of the compound are done by using thin prism method. A four-parameter model is validated by fitting the experimentally measured values of refractive indices, birefringence and average refractive indices of the compound with the theoretical ones. Refractive index and density data are utilized for determination of orientational order parameter. The temperature variation of dielectric permittivities of the compound are measured by a LCR meter. 相似文献
64.
High bit-rate (>10 Gb/s) signals are composed of very short pulses and propagation of such pulses through a semiconductor
optical amplifier (SOA) requires consideration of intraband phenomena. Due to the intraband effects, the propagating pulse
sees a fast recovering nonlinear gain which introduces less distortion in the pulse shape and spectrum of the output pulse
but introduces a positive chirping at the trailing edge of the pulse. 相似文献
65.
66.
Unimodular waveforms x are constructed on the integers with the property that the autocorrelation of x is one at the origin and zero elsewhere. There are three different constructions: exponentials of the form e2 pi na q,e^{2 \pi i n^\alpha \theta}, sequences taken from roots of unity, and sequences constructed from the elements of real Hadamard matrices. The first is
expected and elementary and the second is based on the construction of Wiener. The third is the most intricate and is really
one of a family of distinct but structurally similar waveforms. A natural error estimate problem is posed for the last construction.
The analytic solution is not as useful as the simulations because of the inherent counting problems in the construction. 相似文献
67.
We propose an electronic spin-filter device that uses a nonmagnetic triple barrier resonant tunneling diode (TB-RTD). This device combines the spin-split resonant tunneling levels induced by the Rashba spin-orbit interaction and the spin blockade phenomena between two regions separated by the middle barrier in the TB-RTD. Detailed calculations using the InAlAs/InGaAs material system reveal that a splitting of a peak should be observed in the I-V curve of this device as a result of the spin-filtering effect. The filtering efficiency exceeds 99.9% at the peak positions in the I-V curve. 相似文献
68.
Datta BP 《Rapid communications in mass spectrometry : RCM》2000,14(8):696-705
The simultaneous isotopic analysis of lithium and boron by the Li2BO2+ ion beam method involves measurements of two different molecular abundance ratios (say, Rj+/-delta(j) and Rk+/-delta(k)), and subsequently extensive calculations to arrive at the analyte isotopic ratios (say, L and Y). It is not presently known how the measurement errors (delta(j) and delta(k)) are transformed into the errors of analysis (deltaL and deltaY). This work addresses this question from fundamental considerations. In the literature, the calculations are sometimes simplified using Ri formulae based on Li2B16O2+ ions and then applying correction factors for the actual Li2BO2+ ions, but this procedure is not generally applicable. We show how equations based on true Li2BO2+ ions (with full isotopic variations of all the constituent elements) can be solved, and illustrate the procedure with several examples. These studies show that accuracy of analysis depends not only on the accuracies of measurements, delta(j) and delta(k), but also on the particular isotopic Li2BO2+ ion-pairs (j and k) used as the monitor pairs. Moreover, this dependence is shown to be different for the different isotopic ratios (L and Y) to be determined simultaneously. Therefore, proper selection of monitor molecular pairs is a requirement for avoiding larger (propagated) errors in the analysis. Similar arguments would, in fact, apply to any arbitrarily chosen case of determining two or an even greater number of isotopic abundance ratios (Ei's) by the molecular ion beam method, irrespective of whether the different analyte ratios, Ei's, relate to a single multi-isotopic element, or different elements. 相似文献
69.
The well-characterized, monodispersed nature of reverse micelles formed by sodium bis(2-ethylhexyl)sulfosuccinate/heptane and their usefulness in approximating a membrane-like environment have been exploited to investigate the effect of pH and water pool size on the photophysical properties of hypericin (Hyp). Our measurements reveal two titratable groups of pKa approximately 1.5 and approximately 12.5. These are assigned to the HypH+/Hyp equilibrium (the deprotonation of a carbonyl group) and the Hyp-/Hyp2- equilibrium (the deprotonation of a peri hydroxyl group). The low-energy absorbance maxima of HypH+, of Hyp and Hyp- and of Hyp2- are 583, 594 and 613 nm, respectively. Neither at pH 13 nor at 1 M HCl is the system entirely in the Hyp2- or the HypH+ forms. Ours is the first study of Hyp in reverse micelles as well as the first time-resolved study of Hyp as a function of pH. 相似文献
70.
Anindya Datta Amitava Raychaudhuri Sreerup Raychaudhuri Surajit Chakrabarti 《Zeitschrift fur Physik C Particles and Fields》1996,72(3):449-460
Many extensions of the Standard Model includeSU(2) L ×U(1) Y singlet higgs bosons,h 0, and also vector-like fermions which couple to it. The production and detection possibilities of such singlet neutral scalars at hadron colliders are considered for different scenarios of vectorlike fermions. We find that for some values of masses and couplings, detection at the CERN large hadron collider (LHC) appears to be a distinct possibility, while at the Fermilab Tevatron upgrade theh 0 might be observed only in very favourable circumstances. 相似文献