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1.
V. S. Pavlovich 《Journal of Applied Spectroscopy》2007,74(2):180-187
The effect of dispersion interactions on the electronic spectra of organic compounds is analyzed within second-order perturbation
theory. A formula is obtained which makes is possible to determine the change in the polarizability of the molecules upon
excitation, Δαeg, using data on the effect of the bulk polarizability Pn of the solvent on the position of the electronic spectrum. It is shown that when the solutions are cooled, the long-wavelength
shift of the absorption spectra for the studied anthracenes in alcohols is mainly due to dispersion interactions and is caused
by an increase in Pn. The possibility of using the new formula for Δαeg is demonstrated for anthracenes as an example. It is found that for anthracene, 1-chloroanthracene, 9,10-dichloroanthracene,
9,10-dibromoanthracene, 9,10-diiodoanthracene Δαeg is 16.5, 16.9, 17.2, 18.6, and 20.2 Å3 respectively.
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Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 162–168, March–April, 2007. 相似文献
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Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 50, No. 6, pp. 906–912, June, 1989. 相似文献
4.
V. S. Pavlovich 《Journal of Applied Spectroscopy》1997,64(6):764-777
Polar luminescence probe+polar medium subsystems are considered. True minimization parameters of the free energy F are obtained.
It is shown that Franck-Condon transitions between F-terms of different electronic states are generally not “vertical”. A
complete thermodynamic classification of photoinduced processes of orientational relaxation in the excited S1 and ground S0 states is presented. Depending on the excitation conditions they can be either exo- or endothermic, spontaneous or induced
(not spontaneous), and accompanied by an increase or decrease in entropy. Indifferent processes also take place. Regularities
of shifts of fluorescence spectral bands and burned holes in time-resolved experiments are discussed.
Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated
from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 753–765, November–December, 1997. 相似文献
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V. S. Pavlovich A. P. Stupak L. G. Pikulik D. T. Kozhich T. A. Pavich 《Journal of Applied Spectroscopy》2008,75(3):319-324
The molar extinction coefficient, oscillator strength, natural fluorescence lifetime, and fluorescence quantum yield have
been determined for 9,10-diiodoanthracene in ethanol at 20°C. The temperature effect on the quantum yield was studied in the
range 120–300 K. The fluorescence lifetime was measured at 77 K. During glassification of ethanol, the fluorescence intensity
of 9,10-diiodoanthracene increases by more than 50 times due to the activation nature of the intersystem crossing from the
S1(1B2u+) state. The activation energy and pre-exponential factor for the probability of the intersystem {ie319-01}-crossing are found.
The long-wavelength shift of the absorption spectrum with increasing bulk polarizability of the solvent is interpreted as
evidence of changes in the nonspecific interactions.
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Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 304–308, May–June, 2008. 相似文献
8.
V. S. Pavlovich 《Journal of fluorescence》1997,7(4):321-329
With statistical thermodynamics methods, it is shown that the evolution of a polar luminescence probe + polar disordered medium system after pulse excitation is described by an equation for damped vibrations. From this it follows that in the solvation shell of the excited solute probe, not only synchronous librations but also cooperative jump reorientations of solvent molecules take place, and their damping motion is caused by localized dielectric friction. This collective molecular dynamics is examined as the motion of a quasi-particle called a histon. The histon moment of inertia and mass are determined. The concept of l- and j-histons are also introduced. In terms of this model the full correlation functions for nonequilibrium solvent dynamics are derived. The behavior of steady-state and time-resolved spectra is examined and it is found that the limiting short-wavelength position of the steady-state spectrum at a low temperature and that for time-dependent fluorescence at t 0 are not identical. The histon model has been used for interpretation of the emission band collapse that is observed in long-time evolution experiments. Some other problems of spectral broadening are also discussed. As predicted, sharp expansion of the fluorescence band takes place on an ultrafast time scale due to dephasing of l-histons. 相似文献
9.
E. N. Pavlovich A. S. Bratus 《Moscow University Computational Mathematics and Cybernetics》2012,36(3):137-144
An open replication model with a matrix circulator is considered. The stability and asymptotic behavior of the system depending on the input parameters is studied. 相似文献
10.
Eugeny Nikolaevich Zapolotsky Sergey Pavlovich Babailov Gennadiy Alexandrovich Kostin 《Molecules (Basel, Switzerland)》2022,27(14)
1H NMR measurements are reported for the CD2Cl2/CDCl3 solutions of the Co(II) calix[4]arenetetraphosphineoxide complex (I). Temperature dependences of the 1H NMR spectra of I have been analyzed using the line shape analysis, taking into account the temperature variation of paramagnetic chemical shifts, within the frame of the dynamic NMR method. Conformational dynamics of the 2:1 Co(II) calix[4]arene complexes was conditioned by the pinched cone ↔pinched cone interconversion of I (with activation Gibbs energy ΔG≠(298K) = 40 ± 3 kJ/mol. Due to substantial temperature dependence of paramagnetic shifts, complex I can be used as model compound for designing an NMR thermosensor reagent for local temperature monitoring. 相似文献