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21.
Fast and efficient intramolecular charge transfer (ICT) and dual fluorescence is observed with the planarized aminobenzonitrile 1-tert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6) in a series of solvents from n-hexane to acetonitrile and methanol. Such a reaction does not take place for the related molecules with 1-isopropyl (NIC6) and 1-methyl (NMC6) groups, nor with the 1-alkyl-5-cyanoindolines with methyl (NMC5), isopropyl (NIC5), or tert-butyl (NTC5) substituents. For these molecules, a single fluorescence band from a locally excited (LE) state is found. The charge transfer reaction of NTC6 is favored by its relatively small energy gap DeltaE(S(1),S(2)), in accordance with the PICT model for ICT in aminobenzonitriles. For the ICT state of NTC6, a dipole moment of around 19 D is obtained from solvatochromic measurements, similar to micro(e)(ICT) = 17 D of 4-(dimethylamino)benzonitrile (DMABN). For NMC5, NIC5, NTC5, NMC6, and NIC6, a dipole moment of around 10 D is determined by solvatochromic analysis, the same as that of the LE state of DMABN. For NTC6 in diethyl ether at -70 degrees C, the forward ICT rate constant (1.3 x 10(11) s(-1)) is much smaller than that of the back reaction (5.9 x 10(9) s(-1)), showing that the equilibrium is on the ICT side. The results presented here make clear that ICT can very well take place with a planarized molecule such as NTC6, when DeltaE(S(1),S(2)) is sufficiently small, indicating that a perpendicular twist of the amino group relative to the rest of the molecule is not necessary for reaching an ICT state with a large dipole moment. The six-membered alicyclic ring in NMC6, for example, prevents ICT by increasing DeltaE(S(1),S(2)) relative to that of DMABN.  相似文献   
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Paramagnetic centers generated by swift heavy ion irradiation of LiF crystals could be identified as electrons trapped at regular anion vacancy sites (F centers). Well-resolved electron-nuclear double resonance (ENDOR) spectra resulting from the hyperfine interaction with 7Li and 19F nuclei located in six different shells could be recorded. In order to preserve the millimeter-sized crystals, a cavity-free setup was used for the ENDOR experiments at an electronic Larmor frequency of 240 GHz. Apparently even under conditions of extremely high local energy loss in the ion track, the local density of persistent F centers is still sufficiently low to prevent distortions of the ionic crystal. The spread of hyperfine coupling constants was less than 5 %. Neither in electron paramagnetic resonance (EPR) nor in ENDOR spectra there was evidence for different types of paramagnetic centers. When performing ENDOR by applying the radiofrequency pulse directly after the 3-pulse Mims-type microwave sequence, an anomalous ENDOR effect was observed. The observed “positive” and “negative” ENDOR response can be attributed to efficient hole and anti-hole formation in the inhomogeneously broadened EPR spectrum and can be used to determine the sign of hyperfine coupling constants.  相似文献   
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The beta endpoint energies of the alkaline fission products88–94Rb and139–144Cs have been measured with an intrinsic Ge-detector at the OSTIS fission product separator. The linearity and high resolution of the detector yields an accuracy of up to a few keV. Additional beta gamma coincidence spectra allow the deduction of Qβ-values.  相似文献   
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It is rigorously proved that for nonlinear dynamical systems whose time dependence is described by one dimensional, everywhere expanding maps, the width of broadband noise in the power spectrum is bounded by the generalized entropiesK 2 andK 3, which measure the strength of chaos in this system asK 22K 3.Dedicated to Professor Harry Thomas on the occasion of his 60th birthday  相似文献   
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Molecular orbital X-rays are emitted during ion-atom collisions. The theoretical treatment, numerical results for the Pb + Pb system and a comparison with background radiation like NNB, SEB and γ-decay of Coulomb excited nuclei are presented.  相似文献   
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In this work, two all-fiber interferometric configurations based on suspended core fibers (SCF) are investigated. A Fabry–Pérot cavity (FPC) made of SCF spliced in-between segments of single-mode and hollow-core fiber is proposed. The interferometric signals are generated by the refractive-index mismatches between the two fibers in the splice region and at the end of the suspended-core fiber. An alternative sensing head configuration formed by the insertion of a length of SCF as a birefringence element in a Sagnac loop interferometer is also demonstrated. In this structure, the interferometric signals are generated by interfering two counter propagating beams with different polarization states which propagate through a length of SCF as a birefringence element. The sensitivity to pressure and temperature was determined for both configurations. The results show that the pressure sensitivities are ? 4.68 × 10? 5 nm/psi and 0.032 nm/psi for FPC and Sagnac loop interferometers, respectively. The temperature sensitivity of both structures has been obtained and the results have been discussed.  相似文献   
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