Deactivation of an excited charge-transfer complex II. Influence of rigidity of medium on radiative and radiationless transitions

Fluorescence spectra, quantum yields and decay times for charge-transfer complexes of tetracyanoethylene with benzene, toluene, ortho-xylene and para-xylene in low-temperature glassy solutions of different viscosities have been investigated. It was established that the influence of viscosity or rigidity of medium on charge-transfer fluorescence consists in the decrease of efficiency of radiationless processes when viscosity or rigidity increases. Fluorescence spectra of complexes of tetracyanoethylene with toluene, o-xylene and p-xylene have a composite double-band character at high viscosities of medium. The intensity of both subbands changes in a different way with change of viscosity. The excitation spectra of these complexes are dependent on the wavelength of observation. These facts are discussed in terms of an existence of different orientational isomers of a charge-transfer complex of low symmetry.     

Heavy-atom effect on radiative and radiationless transitions in charge-transfer complexes

The quantum yields of fluorescence and phosphorescence and decay times of fluorescence were measured for a series of charge-transfer complexes of hexamethylbenzene (an electron donor) with various electron acceptors containing heavy (halogen) atoms and the rate constants of different radiative and radiationless transitions were determined. It was found that radiative T₁ → S₀ transition, i.e. the phosphorescence, is strongly enhanced by the heavy-atom effect. The mechanism of the heavy-atom enhancement of charge-transfer phosphorescence is discussed and it is concluded that increasing spin- orbit mixing of radiative T₁ → S₀ charge-transfer transition with singlet-singlet, locally excited transition of acceptor molecule is responsible for the observed effects.     

Influence of the radiationless transitions on an intensity of the optical radiation emitted by excited atoms ejected from solids by an ion beam

The excited atoms of the target material are ejected during an ion bombardment of solids. These atoms belong to one of two velocity groups — fast or slow. The fast atoms arise in binary collisions of bombarding ions with target atoms and the slow ones are knocked out as a result of a sputtering process. Excited atoms flying off the surface intersect the solid-vacuum boundary and can transfer their excitation energy in the radiationless transitions mainly of the resonance ionization type. The probability of this process depends strongly on the electronic energy level structure of solids and a velocity of ejected atoms. On this statement our method of the electronic energy level structure of solids study is based by means of investigation of excited atoms velocity spectrum. On the results of paper [4] we remark that in their experimental conditions the surface of the lithium target was apparently strongly oxidized. Using our method and results of paper [4] we can estimate the energy width of the conduction band of Li₂O to 0.4 eV. In general the cascade corrections to the mean life times of excited atoms may be important and one can take them into account. The detailed analysis of the influence of the cascade corrections to the mean life times of upper excited states of some TiI lines (λλ 5210 Å, 5064 Å, 4682 Å, 3981 Å, 4533 Å, 4856 Å) was carried out. It was found that in the case when our method was applied to determination of the work function of metallic titanium the cascade corrections either are negligible or not necessary.     

Nonempirical investigation of the probability for radiationless transitions. I

The probability for radiationless T₁–S₀-transitions was investigated. An expression for the Franck-Condon factor is obtained by means of exact integration, on the basis of the theory of multiphonon transitions. This expression is utilized for the investigation of the radiation-less T₁–S₀-transition in the formaldehyde molecule. It is found that the transition mentioned does not play a large role.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 11, pp. 32–37, November, 1971.     

硅（Si）原子高激发态能级自然辐射寿命的测量

能级的自然辐射寿命是确定跃迁几率和振子强度所需的重要参数. 目前,硅原子高激发态能级自然辐射参数的实验数据还很缺乏,因此本文运用时间分辨激光诱导荧光和激光烧蚀等离子体技术,测量了硅原子位于47351.55 ~ 63844.65 cm?1之间的14个高激发态能级的自然辐射寿命. 实验结果分布在8.7 ~ 43.4 ns之间,测量误差均小于10%,其中9个能级的结果属于首次报道. 本文结果与可靠的分支比数据相结合可确定相关能级的跃迁几率和振子强度实验值.     

Nonempirical investigation of the probability for radiationless transitions. II

The dependence of the probability for radiationless transitions on the temperature and energy gap is investigated using the theory of multiphonon transitions. The temperature dependence is found to be extremely weak in the case limited to interval vibrations.Translated from Izvestiya VUZ. Fizika, No. 1, pp. 23–27, January, 1972.     

Influence of solvent polarity on the photophysical properties of arylethylene derivatives

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 51, No. 4, pp. 659–665, October, 1989.     

Theoretical studies on the anisotropy of the first hyperpolarizabilities of one- and two-dimensional charge-transfer molecules: role of solvent polarity

The effects of solvent polarity on the geometry and static first hyperpolarizability of one- and two-dimensional charge transfer molecules based on para-nitroaniline (PNA) and 1,3-diamino-4,6-dinitrobenzene (DADB) were studied using a polarizable continuum model (PCM) at the B3LYP/6-31+G(d,p) level of theory. The inclusion of solvent does not change the geometry significantly, but produces a change in the calculated results of the electronic structures and nonlinear optical properties. It is found that solvent polarity has an important influence on the first hyperpolarizability, whereas its influence is negligible on the nonlinearity anisotropy parameter both for PNA and DADB, due to the fact that the off-diagonal component and the diagonal component of the first hyperpolarizability possess similar solvent effect characteristics.     

Influence of excited configurations on the intensities of electric-dipole transitions of rare-earth ions

The theory of induced electric-dipole transitions of rare-earth ions in crystals and glasses is improved by taking into account the third-order effects of perturbation theory with respect to the energies of virtual excitations of 4f electrons to the 5d states. Since the energy regions of excited 4f ^{N ? 1}5d states are usually superimposed with the charge-transfer bands, the effects caused by a virtual transfer of an electron from the outer shells of ions of the surroundings (ligands) to the unfilled 4f ^N shells are also considered. The Pr³⁺, Sm³⁺, and Eu³⁺ ions are considered as examples. It is found that some difficulties inherent in the Judd-Ofelt calculation scheme are successfully overcome. The agreement of the calculated results with the experimental data improves.     

Probabilities of radiative dipole transitions of parahelium in an electric field

Quadratic Stark corrections to the wave functions, matrix elements, and probabilities of transitions between the singlet states ¹ S ₀ and ¹ P ₁ of helium atoms are calculated. The coefficients of the polynomials that depend on the effective principal quantum number of the upper level v _f and that approximate the numerical values of the polarizabilities, the quadratic corrections to the wave functions, and the probabilities of transitions to highly excited Rydberg states with large v _f are determined. The results of calculations testify that the probabilities of all σ transitions n _i ¹ S ₀ → n _f ¹ P ₁ and π transitions to the states with n _f > n _i /2 are decreased with increasing electric field strength, except for the transition 2¹ S ₀ → 2¹ P ₁, whose probability increases both for σ and for π transitions.     

Influence of complex component and particle polydispersity on radiative properties of soot aggregate in atmosphere

The effects of morphological structure, water coating, dust mixing and primary particle size distribution on the radiative properties of soot fractal aggregates in atmosphere are investigated using T-matrix method. These fractal aggregates are numerically generated using a combination of the particle-cluster and cluster-cluster aggregation algorithms with fractal parameters representing soot aggregate in atmosphere. The radiative properties of compact aggregate notably deviate from that of the branched one, and the effect of morphology changes on the radiative properties in wet air cannot be neglected. However it is reasonable to use realization-averaged radiative properties to represent that of the aggregates with certain morphology. In wet air, the scattering, absorption and extinction cross-section and symmetry parameter of soot aggregates coated with water notably increase with water shell thickness. The mixing structures of dust have little effect on radiative properties of aggregates, but the volume fraction of dust has an obvious effect on extinction, scattering and absorption cross-section of aggregates when the size parameters are above the Rayleigh limit. Although the primary particle size distribution of soot aggregate has mild effect on the scattering albedo and asymmetry parameter, the deviations of the extinction, scattering, absorption cross-section among the three size distributions are significant in this study. The size distribution has a significant effect on forward scattering of phase function, while the effect can be neglected as the size parameter approaches to the Rayleigh limit.     

Theory of radiative and nonradiative transitions for semiconductor nanocrystals

Existing calculations on the radiative and nonradiative transitions in semiconductor crystallites are reviewed with particular emphasis on indirect band-gap materials like silicon for which the quantum confinement effects are more spectacular. It is shown that the crystallite gaps and radiative recombination rates can be predicted with fair accuracy. Effects related to atomic relaxation in the excited state (Stokes shift) are calculated and it is shown that small enough crystallites lead to self-trapped excitons which provide another source of luminescence, much less dependent on size effects. Nonradiative processes are then examined: intrinsic, due to Auger recombination, and extrinsic, due to dangling bond surface states. Both are found to play an essential role in the interpretation of experimental data. Finally, dielectric screening is studied, justifying the use of a reduced internal dielectric constant and providing an estimate of the Coulomb shift due to charging effects.     

Influence of solvent polarity and temperature on dual fluorescence of 10,10′-dibromo, 9,9′-bianthryl

Fluorescence of 10,10′-dibromo, 9,9′-bianthryl (DBrBA) in solvents of different polarities (n-hexane, dibutyl ether, tetrahydrofuran, and acetone) has been investigated as a function of temperature. Changing of the solvent and variation of temperature modifies the ratio of local (LE) and charge transfer (CT) fluorescence quantum yields. From the basic fluorescence data (quantum yields, lifetimes, ratio of CT to LE fluorescence quantum yields) the temperature-dependent equilibrium constants for the charge transfer process in the excited singlet state were calculated and discussed on the basis of the modern electron transfer theories. It has been found that the intersystem crossing in DBrBA in nonpolar n-hexane, leading to the population of the lowest triplet state, proceeds via the third triplet state. It has been confirmed by the fluorescence measurements and quantum mechanical calculations. Surprisingly, the experimentally obtained intersystem crossing rate constants are very weakly dependent on temperature. Thus, the electron transfer reaction leading to the population of the molecular triplet state is probably an adiabatic reaction with a rate constant controlled by the dielectric relaxation of the solvent.     

Two-dimensional images of radiative and metastable excited stateradial profiles for an inductively coupled plasma in argon

Inductively coupled plasma (ICP) was shown to be characterized by a substantial degree of stepwise excitation due to a large density of metastable atoms and an even larger population of electrons. The kinetics of metastables strongly affects the structure of the discharge and we have applied laser absorption spectroscopy to establish the density profile of argon metastables Ar(1s₅) in a single turn coil geometry. At the same time the radial profiles of the radiative Ar(3p₅) state obtained by using a computer-aided tomography are significantly different indicating the effect of electron induced quenching and stepwise processes in kinetics of the two states     

Calculation of collisional and radiative transition probabilities between excited argon levels

Average radiative transition probabilities for argon atoms have been calculated for transitions between 24 levels in two groups characterized by the atomic core terms ²P_1/2 and ²P_3/2 by using the method of Bates and Damgaard. The results are compared with data in the NBS tables (Wiese et al.) and with those of Katsonis and Drawin. We find satisfactory agreement for the order of magnitude, even for transitions between lower lying levels. Parameters, which appear in Drawin's semiempirical cross-section expressions for electronic excitation of optically allowed and parity-forbidden transitions, are determined with the multipole expansion method proposed by Sobel'man for transitions between the specified levels. Most of these are easily obtained, but the method must be improved for transitions between levels having the same azimuthal quantum number because the summation over the constituent terms does not converge.     

Absorption and fluorescent properties of pyrylium compounds: I. The nature of electronic transitions and structural rearrangement in the excited state

The localization of molecular orbitals in 2,4,6-substituted derivatives of pyrylium is studied. The conformation of three asymmetrical molecules with oxyethyl substituents in positions 2 and 4 and different substituents in position 6 of the pyrylium ring is calculated by the AM1 method. The localization of the four upper occupied and two lower unoccupied MOs is determined, the fragment localization numbers are found, and the energies of five optical transitions, localization numbers, and the numbers of charge transfer between fragments are calculated. The conformation analysis of molecules in the S ₀ and S ₁ states is performed. Solid and liquid pyrylium solutions of different viscosity and polarity are experimentally investigated. The absorption spectra are recorded and absorption cross sections are measured, as well as fluorescence spectra and fluorescence anisotropy spectra. The following conclusions are made. In nonplanar molecules of pyrylium salts, four absorption transitions are localized at different parts of the molecule containing the pyrylium ring and one of the substituents. Upon excitation of molecules with complex substituents in position 6, the molecular fragment in position 2 turns around. This results in a flattening of the molecular fragment containing the pyrylium ring and substituents 2 and 6 on which the fluorescence transition is localized. The rearrangement involves the lowamplitude motion; it occurs almost without a loss of the excitation energy and only slightly affects the localization of molecular orbitals. As a result, two excited conformers are formed that possess close absorption and fluorescence properties. The radiative transitions in these conformers completely determine fluorescence of liquid solutions of any viscosity, including glycerol solutions. Strong solvatochromism is related to the nonplanar structure of stable pyrylium molecules, whereas the weak solvatochromism of liquid solutions is caused by localization of radiative transitions on a planar fragment of unstable fluorescing conformers.