Triplet-triplet transfer of electronic excitation energy in vapors of organic molecules

The rate constants of the triplet-triplet (T-T) transfer of energy of the electronic excitation obtained in the gas phase for two sets of donor-acceptor pairs with various spectral characteristics are compared with those predicted by the theories of nonradiative transitions. The rate constants K _TT and efficiencies β_DA of the T-T transfer are estimated from quenching of the phosphorescence of biacetyl by aromatic hydrocarbons (anthracene, 9-methylanthracene, 9,10-dimethylanthracene, 9-phenylanthracene, pyrene, and chrysene) and from quenching of the delayed fluorescence of benzophenone, 4-phenylbenzophenone, anthraquinone, carbazole, and naphthalene by biacetyl, as well as from the sensitization of phosphorescence of biacetyl by these compounds. The causes of the broad variations of β_DA in the gas phase from 0.35 (biacetyl-anthracene) to 10^?4 (biacetyl-chrysene) are discussed for the studied donor-acceptor pairs, which differ in the exothermicity of the process and in the configuration of the lowest triplet levels of the molecules participating in the transfer. The dependences of the transfer rate constants K _TT on the free energy change ΔG (the range from 0.4 to ?1.7 eV) are analyzed. It is shown that, in gas-phase systems, K _TT increase with the exothermicity of the transfer, attain a highest value, and then decrease in the range of negative ?ΔG. The observed differences in the experimental values of β_DA are discussed in terms of changes in the free energy ΔG of the process, in the energy of rearrangement of the nuclear configuration of the molecules during the transfer, and in the matrix elements of the interaction.     

Rotational excitation of H2 and N2 molecules by electron impact

The rotational excitation of the H₂ and N₂ molecules from (J→J+2,J=0) and (J→J+2,J=1) states by electron impact is studied, in the framework of the regional-plane-wave approximation. The empirical cut-off parameterρ, involved in these calculations, is varied to give the best fit to the experimental data of Srivastava and co-workers.     

Triplet-triplet transfer of electronic energy upon nonequilibrium vibrational excitation of triplet molecules

The specific features of the triplet-triplet (T-T) transfer of electronic excitation energy in a gas phase upon nonequilibrium vibrational excitation of the triplet molecules of a donor were studied for an anthraquinone-diacetyl donor-acceptor pair using the time-resolved slow fluoresence of anthraquinone and sensitized phosphorescence of diacetyl. It is shown that in the gas phase, which allows regular control of the number of collisions, competition between the processes of T-T transfer and intermolecular vibrational relaxation is observed for nanosecond time resolution. The T-T transfer rate for the molecular system investigated exceeded the rate of intermolecular vibrational relaxation k_V in the triplet state T₁ of the donor. The effectiveness of the T-T transfer of energy by vibrationally excited molecules turned out to be higher than the effectiveness of transfer by thermalized ones, but even the highest of them was much less than unity. An increase in the equilibrium temperature of vapors led to a decrease in the effectiveness of transfer for both vibrationally excited and thermalized triplet molecules, thus indicating the importance of the collisional complex in the intermolecular process studied. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 474–479, July–August, 2000.     

Dissociative excitation of the fluoromethanes by electron impact

Emission spectra following electron impact on molecules of the homologous series of fluoromethanes CH_xF_4-x with x=0-4 have been investigated from the near infrared at 700 nm to the ultraviolet VUV-spectral region at 100 nm. Earlier experimental data for the visible and ultraviolet spectral region were revised and evaluated again on the basis of reliable new data for the dynamic viscosity of the molecules. The measurement of absolute and relative cross-sections were systematically extended into the VUV region from 100 nm to 200 nm. The examination of atomic lines as well as molecular band systems in the VUV gives further insight into the dissociation mechanism and shows that many excited levels even of atomic and molecular species cannot be populated directly, but only by transitions from higher-lying energy levels. Simple steric effects can be distinguished from more complex transition phenomena. Received: 25 February 1998 / Revised: 29 May 1998 and 18 June 1998 / Accepted: 23 June 1998     

Vibrational excitation in the nitrogen molecule by electron impact

The European Physical Journal D - We report an experimental study on the effect of detuning on velocity-induced population oscillation (VIPO) for a Doppler mismatched double resonance. The double...     

On the mechanism of electronic excitation energy migration in organic liquids

The rate constant for electronic excitation energy transfer from toluene toa fluorescent indole measured as a function of temperature indicates unequivocally that the excitation energy migration is entirely due to resonance interaction and not due to excimer formation-dissociation.     

Two-electron excitation in helium-like ions by electron impact

Calculation of cross-sections for the two-electron excitation in helium-like ions by electron impact employing Coulomb-Born-Oppenheimer (CBO) approximation is presented. Analytical expressions for the differential and total scattering cross-sections without using partial wave expansion of the wavefunction reported earlier have been used. The total and differential scattering cross-sections for each of the excitations 1s ^{2 1} S* → 2s ^{2 1} S ^e , 2s2p ^1.3 P ⁰, 2p ^{2 1} S ^e ,³ P ^e,¹ D ^e in Be²⁺ and B³⁺ are computed. Results for Li⁺ reported earlier are also included for comparison.     

Ionization of diatomic molecules by electron impact

An analytical expression for the amplitude of ionization of the hydrogen molecule by electron impact in the first Born approximation with a one-center Coulomb continuum wave function is derived. The case where the incident electron energy is much greater than the ejected electron energy is considered. The molecular wave functions were constructed in the approximation of linear combination of atomic orbitals with overlapping configurations. The role of the orthogonalization of the initial and final wave functions of the active electron of the target is elucidated. The triple differential ionization cross sections for the different orientations of the molecular axis and that averaged over all orientations are calculated. The secondary electron angular distribution is represented in the form of three-dimensional images. A comparison with the results of other theoretical calculations and experimental data is performed.     

Nonradiative triplet-singlet transfer of electronic excitation energy between dye molecules in the vicinity of the silver-film surface

Nonradiative triplet-singlet transfer of electronic-excitation energy between molecules of organic dyes (erythrosine and methylene blue) in a polymer film that is deposited on the surface of a silver layer is experimentally studied. It is demonstrated that the energy-transfer efficiency in such a system is lower than the efficiency in the samples without metal layers. The results of the proposed mathematical model are in qualitative agreement with the experimental data.     

Glauber exchange effect in the excitation of hydrogen by electron impact

The Glauber exchange effect is included into the calculations of differential cross sections in an analysis of 1–2 excitation of the hydrogen atom by electron impact within the conventional Glauber theory. An improvement of the theoretical results is obtained.     

绝对测量He原子快电子碰撞双激发的电子关联动力学

应用高分辨快电子能量损失谱仪 ,绝对测量了He原子各种光学允许和光学禁戒的双电子激发过程的动量转移依赖特性 ,报道了作为动量转移函数的以内禀关联量子数K ,T和A表征的电子态 2(0 ,1 ) 2 1 Po,2 (1 ,0 ) 2 1 Se和 2(1 ,0 ) 2 1 De的Fano参数q ,fa,ρ2 ,f和S ,同时对 2(- 1 ,0 ) 2 1 Se和 2(1 ,0 ) 2 的波函数作出定性检验 .从而在实验上通过激发动力学过程研究了电子关联效应     

CIDNP investigation of electron excitation energy transfer in the photolysis of isotope-mixed molecules of benzophenone in cyclohexane-D12

Isotopic effects arising in the photolysis of benzophenones-H₁₀/D₁₀ mixtures in cyclohexane-D₁₂ at room temperature were studied by CIDNP method. Nonlinear dependences of these effects on a relative concentration of benzophenone-D and benzophenone-H molecules have been obtained. To interpret the results, a theoretical model involving intermolecular and intramolecular energy transfers and radical-pair mechanism of CIDNP formation has been proposed. Nonlinearity of isotopic effects is determined by the difference in electron excitation energy between benzophenone-D and benzophenone-H molecules.     

Carbon K-shell excitation in acetone by 2.5 keV electron impact

The energy loss spectrum of 2.5 keV electrons, scattered by gaseous acetone through small angles, has been obtained in the region of the carbon K-edges. Discrete structure observed below the ionization threshold is interpreted as arising from the promotion of a carbon K-shell electron to Rydberg orbitals. Broad peaks observed above the K-edges are associated with the simultaneous transitions of a carbon K-shell and valence shell electrons (shake-up and shake-off processes).     

Cross sections for excitation of the lutetium atom by electron impact

Journal of Applied Spectroscopy -