Estimate of factors affecting the relative intensity of components of the doublet in the delayed fluorescence spectrum of coronene in n-octane at 77?K

We propose a procedure for determining the contribution from the concentrations of triplet molecules and their interaction constants to the intensity of delayed annihilation fluorescence of isolated molecular pairs. We have used the proposed procedure to determine the contribution of these quantities to the intensity of the components in the doublet in the quasi-line delayed fluorescence spectrum of coronene in n-octane at 77 K.     

Effect of concentration,temperature, and freezing rate on the phosphorescence parameters of acenaphthene in <Emphasis Type="Italic">n</Emphasis>-hexane matrices

The effect of the concentration, temperature, and freezing rate on the spectra, kinetics, and intensity of phosphorescence of acenaphthene in polycrystalline n-hexane matrices has been studied. The specific features of the transformation of quasi-lines in the phosphorescence spectrum of molecules embedded in an n-hexane crystal lattice into broad molecular bands at high concentrations of the solution (~10^?1 mol/L) have been considered. It has been demonstrated that a distortion of the n-hexane crystal lattice at a high concentration of embedded acenaphthene molecules can be a cause of the observed transformation of the quasi-line spectrum.     

Diffuse component of the fluorescence spectrum of anthracene vapor as a function of the frequency of the exciting radiation

The paper discusses experimental results for the frequency dependence of the diffuse component of the fluorescence spectrum of anthracene vapor that accompanies quasi-lines for excitation in the frequency zone of excitability of the quasi-line spectrum. Data for the anthracene molecule in the gas phase are compared with results for aromatic molecules in vitreous matrices at low temperatures. State Institute of Applied Optics, Federal Scientific and Production Center, 2, Lipatov Str., Kazan, 420075, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No, 5, pp. 645–648, September–October, 1999.     

Dual fluorescence of <Emphasis Type="Italic">N</Emphasis>-pyrrolobenzonitrile in extended polyvinyl alcohol films

The possibility of radically changing the conditions for charge transfer (CT) photoreaction in N-pyrrolobenzonitrile molecules in polymer matrices of polyvinyl alcohol (PVA) under their extension has been demonstrated. The fluorescence spectrum of N-pyrrolobenzonitrile in PVA has two characteristic bands in the UV and visible spectral ranges, which are indicative of the CT reaction that occurs in the excited state. Extension significantly reduces the intensity of the UV band, the contribution of which in unstrained samples is comparable with the violet fluorescence intensity. Even a single extension of PVA films significantly reduces the intensity of the UV band, while a sixfold extension dramatically enhances this effect. In the latter case, the fluorescence spectrum contains a strong CT band whose relative intensity exceeds that for highly polar aprotic solvent acetonitrile by a factor of five. The data obtained indicate that, using extension, one can change the main intermolecular factors affecting the CT rate in PVA samples.     

汞原子塞曼效应分裂谱线相对强度的测量

为了研究塞曼效应分裂谱线的相对强度,分析了Hg(546.1 nm)谱线能级在外磁场中的分裂情况,详细给出了分裂能级的量子数分布和理论相对强度;在此基础上采用CCD拍摄了分裂谱线干涉圆环的图像,并对其进行了强度分析,通过图像强度处理得到各分裂谱线相对强度与理论分析结果十分接近;表明采用CCD图像技术能较好的分析塞曼效应现象和规律.     

EPR evidence of the low temperature phase transition in C60

A standard EPR technique has been applied to perform temperature studies of polycrystalline samples of C₆₀ fullerene. A comparison of the three main parameters of EPR spectra obtained for a C₆₀ sample before and after (solvent free) purification has been made in temperatures from 4 to 300 K. When compared to the spectrum of the as-obtained (crude) sample the spectrum of the purified sample revealed considerable changes i.e. an increase in the EPR signal intensity and evidence of a phase transition at about 90 K. This transition is proved to be related to the two processes: freezing of the orientational motion of C₆₀ molecules and redistribution of the positive and negative charge observed as paramagnetic centres localized on C₆₀ molecules.     

Photostimulated electron transfer and its action on paramagnetism of Sp<Subscript>3</Subscript>Cr(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript> single crystals

The effect of irradiation by ultraviolet light on the effective magnetic moment of a paramagnetic single crystal based on photochrome spiropyran (Sp) and chromium oxalates Sp₃Cr(C₂O₄)₃ molecules is detected. It is shown that the deviation of the temperature dependence of the magnetic moment from the Curie law is caused not by the exchange interaction, but by electron redistribution between Cr³⁺ and Cr⁴⁺ ions and spiropyran molecules Sp⁰ and Sp⁺. Analysis of the angular dependence of EPR spectra makes it possible to determine the contribution of Cr³⁺ ions to the magnetic properties of the crystals and to determine the crystal field parameters D = 0.619 cm⁻¹ and E = 0.024 cm⁻¹. Irradiation of hydrated samples by ultraviolet light leads to intensity redistribution of EPR lines attributed to Cr³⁺ and Sp⁰. Thermally stimulated paramagnetism of triplet states of spiropyran ions Sp⁺ and the SpI salt is observed.     

Determination of the helium-4 mass in a Penning trap

The determination of the rotational quadrupole alignment of diatomic molecules via REMPI detection is investigated. In this process a high focal intensity usually increases the detection probability. At high intensities the AC Stark effect may cause a splitting of the normally degenerate m_J sublevels of a rotational state J beyond the spectral width of the exciting radiation. This leads to a selective detection of only certain m_J states with the consequence that deduced alignment factors can be misleading. From the theoretical considerations line profiles are explicitly calculated for dynamic polarizabilities which represent the B ¹Σ⁺ _u←X ¹Σ⁺ _g transition of H₂, in order to fit an experimental (3+1) REMPI spectrum and to predict (1+1') line shapes as a function of laser intensity. It is further shown that the deduced quadrupole alignment factor A ₀ ⁽²⁾ is significantly changed by the second order AC Stark effect when the intensities are chosen high enough to observe asymmetric broadened line profiles. Different combinations of relative linear polarizations of the exciting and ionizing laser beams are discussed. Received 1st August 2000 and Received in final form 2 May 2001     

Line spectra of guest molecules in n-paraffin matrices and the theory of the impurity centre

The quasi-line spectra of guest molecules in organic matrices are analyzed by the adiabatic theory of impurity centres. The effects of changes of the normal coordinates of the oscillators during photo-transitions are included. Weak, intermediate, and strong coupling are considered. The principal effects of temperature are explained.     

Population inversion on vibrational transitions of molecules under nonresonant optical excitation

The possibility of obtaining a population inversion on vibrational transitions of molecules through nonlinear effects when the pump radiation is absorbed in the wings of spectral lines is investigated theoretically. We show that a population inversion can be produced in molecules on vibrational transitions when intense pump radiation is absorbed in the blue wing of the R branch of the vibrational-rotational molecular spectrum. This effect is related to inequality of the probabilities of the absorption and stimulated emission of radiation and is attributable to collisional transitions between rotational levels. We have ascertained that the larger the rotational constant of the molecule and the higher the pump radiation intensity, the higher the effective frequency of the collisions that give rise to a population inversion. Using the carbon monoxide (CO) molecule as an example, we show that when intense (∼1010 W cm⁻²) pump radiation is absorbed in the blue wing of the R branch, a noticeable population inversion can be produced and the gain at the center of the R and P branches of the molecular spectrum can reach 0.011 and 0.250 cm⁻¹ at temperatures T = 300 and 100 K, respectively.     

Aurones: Small Molecule Visible Range Fluorescent Probes Suitable for Biomacromolecules

Aurones, derivatives of 2-benylidenebenzofuran-3(2H)-one, are natural products that serve as plant pigments. There have been reports that some of these substances fluoresce, but little information about their optical properties is in the literature. In this report, series of aurone derivatives were synthesized as possible fluorescent probes that can be excited by visible light. We found that an amine substituent shifted the lowest energy absorption band from the near-UV to the visible region of the electromagnetic spectrum. Four amine-substituted aurone derivatives were synthesized to explore the effect of this substituent on the absorption and emission properties of the aurone chromophore. The emission maxima and intensities of the molecules are strongly dependent on the nature of the substituent and the solvent polarity. Overall, the emission intensity increases and the maximum wavelength decreases in less polar solvents; thus, the aurones may be useful probes for hydrophobic sites on biological molecules. A limited investigation with model protein, nucleic acid and fixed cells supports this idea. It is known that the sulfur analog of aurone can undergo photo-induced E/Z isomerization. This possibility was investigated for one of the aminoaurones, which was observed to reversible photoisomerize. The two isomers have similar absorption spectra, but the emission properties are distinct. We conclude that appropriately substituted aurones are potentially useful as biological probes and photoswitches.     

The intensity distribution in the CH(A2Δ − X2Π) spectrum produced by electron impact on acetylene

The intensity distribution in the rotational and vibrational structure of the CH(A²Δ ? X²Π) spectrum, formed by dissociative excitation of acetylene by electron impact, is analysed. This spectrum is built-up from three overlapping bands, namely, the 0-0, 1-1 and 2-2 bands. The intensity distribution in the rotational structure of the 0-0 band is determined by an analysis of the free rotational lines of the R-branch. The intensity distribution in the other bands is analysed by a comparison of the spectrum with a spectrum simulated on the computer. In this way, the overlap of the various rotational and vibrational transitions is taken into account. It turns out that the distribution of molecules over the rotational levels can be described by assuming one Boltzmann distribution for each vibrational level.     

Crystal-field induced mixing of electron states in C60 crystals at high pressure

Optical absorption spectra of thin fullerene (C₆₀) crystals in the range 1.7 to 3.8 eV have been measured at T=300 K and at pressures up to 2.5 GPa. The spectrum shifts toward the red with pressure, and the electron absorption intensity is redistributed among its bands. The intensity of the band associated with the lowest direct electron interband transition monotonically increases with pressure, whereas the intensity of the upper interband feature decreases. Bands related to weak edge absorption in the range between 1.7 and 2.2 eV gradually merge with the band associated with the lowest interband transition, whose intensity rises with pressure. A similar redistribution of intensity among electron transition bands has been observed when comparing the spectrum of an isolated C₆₀ molecule and that of a C₆₀ crystal. The results indicate that the crystal-field induced mixing of electron states is present in solid C₆₀, and they can be discussed in terms of the Craig-McClure model, which was suggested to describe crystal-field induced mixing of electron states in anthracene and naphthalene molecular crystals. Zh. éksp. Teor. Fiz. 113, 313–322 (January 1998)     

超声空化对丙酮激光喇曼光谱的影响

本研究设计了一种可吸入超声的喇曼光谱样品池,对丙酮的激光喇光曼谱的检测表明,超声空化降低了喇曼光谱的强度,我们认为,超声空化减少了激光光路上参与散射的丙酮分子数是光谱强度降低的主要原因。     

双原子分子多光子电离强场效应的含时波包动力学研究

强激光非线性条件下分子的多光子电离过程呈现出较为明显的强场效应.由于这种效应不能用传统的量子微扰论来处理,“缀饰态”模型方法提供了物理图象清晰的处理光与物质相互作用的方案.本文基于含时波包动力学的基本理论,将激光场看作经典场,利用“缀饰态”模型研究了强场下双原子分子(NO、RbI等)的多光子电离过程.研究表明,激光场的强度、泵浦-探测脉冲延迟时间等对多光子电离光电子能谱的形状有着重要的影响,而这种影响是由光诱导势引起的.另外,在研究具有两个连续态的RbI体系时,自电离现象的发生也与势能面的交叉密切相关,并受外场强度的影响.本文计算模拟外场中分子的光电子能谱时所得到的强场效应对理解和实现原子分子过程的激光操控具有重要的意义.     

Effect of spin and charge fluctuations on the electronic structure of ferromagnetic compounds based on rare-earth metals (on an example of EuO)

The influence of spin and charge density fluctuations on the electronic structure is studied for the generalized fd-model. It is demonstrated that these fluctuations lead to electronic spectrum transformation and redistribution of electrons between f- and d-states, thereby giving rise to electronic phase transformations. It is established that these phenomena are observed in ferromagnetic and paramagnetic regions. A detailed analysis is performed on an example of the EuO ferromagnetic semiconductor.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 100–104, October, 2004.     

Temperature-induced changes in the EPR spectrum of the magnetic center in kaolin

Studies of kaolin have revealed an effect characterized by an unusual temperature-induced change of the EPR spectrum of the Fe3+ ion, which is the magnetic probe in kaolin-clay. At low temperature (T=4.2 K) a resonance line with an effective g-value g1=4.13 +/- 0.16 is observed. At high temperature (T=288 K) one observes a resonance line with the effective g-value g2=2.15 +/- 0.1. The transition from the low- to high-temperature spectrum is gradual and it is accompanied by a redistribution of the absorption intensity. The observed properties of the temperature dependence of the EPR spectrum are characteristic of systems with a multiminimum potential.     

Neutral particle emission from zinc oxide surface induced by high-density electronic excitation

Emission of neutral zinc and oxygen atoms and oxygen molecules emitted from zinc oxide surface by laser irradiation have been measured. It is found that the emission intensity starts to increase when the laser intensity exceeds a certain threshold value, indicating that the particle emission is a high density electronic excitation effect. The energy spectrum of emitted particles is found not to follow the Maxwellian distribution.     

Microwave radiation in the upper atmosphere of the earth during strong geomagnetic disturbances

The influence of N₂ and O₂ molecules on spontaneous microwave radiation spectrum was studied over the decimeter range. This radiation appears in the D and E upper earth atmosphere layers during strong magnetic storms. It was shown to be caused by radiation transitions between medium-perturbed orbitally degenerate Rydberg atom and molecule states A** that occur without changes in the principal quantum number, δn = 0. The available experimental data were used to calculate the dependences of orbitally degenerate state populations on the density of medium and electron flux and temperature. Effective radiation bands were constructed for transitions between highly excited quasi-molecule levels A**N₂ and A**O₂. The emission spectrum was shown to be inhomogeneous and contain three frequency regions in which a noticeable decrease in the intensity of radiation occurred. The physical reason for the formation of these regions was a shift of the emission spectra of quasi-molecules containing unexcited N₂ and O₂ molecules. The frequency profiles of radiation intensity within these frequency regions were calculated as depending on the storm level. Radiation profiles were shown to noticeably change as the storm level increased, they strongly increased close to the right region edge corresponding to high transition frequencies. Nonmonotonic behavior of this profile in the middle of the lower region was observed; this was related to emission spectrum inhomogeneity. A sharp increase in radiation intensity as the magnetic storm level increased occurred in the region of frequencies situated close to the right edge of the upper region (50–100 GHz), which was most interesting for biophysical studies of the action of microwave radiation on living organisms during strong geomagnetic disturbances.