Laser excitation of positronium in the Paschen-Back regime

Zeeman mixing of singlet and triplet 2P states of positronium (Ps) atoms, followed by decay back to the ground state, can effectively turn a long-lived triplet atom into a short-lived singlet state, which would seem to preclude laser cooling of Ps in a magnetic field. Here we report experiments which show that, in fact, because of the large splitting of the n=2 states in a high magnetic field (the Paschen-Back regime), the amount of such mixing diminishes approximately exponentially with an increasing magnetic field >0.01 T and is essentially eliminated above ～2 T. Thus, laser cooling of Ps should be feasible at high fields, which will facilitate the production of a Ps Bose-Einstein condensate.     

Fluorescence quenching as a method of identification of the character of photoreactions in excited states of molecules

We consider the steady-state monochromatic excitation of a luminophore that has fluorescent products. We consider how the fluorescence of singlet states is affected by different means of quenching highlying excited states such as quenching with impurities, temperature quenching, and shortening the lifetime with induced transitions in the light field. We show that the use of different methods of fluorescence quenching opens new possibilities for studying photoreactions that proceed via excited singlet states. Our consideration concerns a wide range of primary photoprocesses, such as electron density redistribution (internal electron transfer) in the excited state, protolytic reactions, intramolecular proton transfer (phototautomerization), hydrogen bond formation, intermolecular relaxation of molecules in solutions, and formation of excimers and exciplexes. The obtained relations have been used to analyze experimental fluorescence spectra of solutions of some organic compounds, including derivatives of 3-hydroxyflavone and 3-aminophthalimide, subjected to quenching by different methods.     

Dynamic fluorescence quenching and the highest excited states of molecules

The dynamic fluorescence quenching in organic molecules, or quenching of the second kind according to Vavilov’s classification, is an efficient method of investigating excited states in solutions and is widely used in various fields. The effect of quenching on the intensity of the fluorescence from the first and higher singlet states of organic molecules is studied. The results may serve as a basis for determining the nature of the short-wavelength luminescence and can be used to distinguish the S _n fluorescence from the comparably intense luminescence of impurities, which is a very important problem when investigating such emissions. A method for obtaining dynamic quenching by specially chosen quenchers is proposed. The method is based on an experimentally found strong increase in the constants of bimolecular collisions of luminophore and quencher molecules when the luminophore is excited through the highest singlet states.     

醌对卟啉荧光猝灭的溶剂效应

测定了在室温和未脱氧条件下不同浓度的苯醌(BQ)对卟啉衍生物四苯基卟吩(TPP),四苯基卟吩锌(ZnTPP)激发一重态的猝灭.由猝灭而引起的荧光强度的变化和荧光寿命的变化均可用Stern-Volmer关系式描述.由此根据寿命计算出的猝灭常数均比据荧光强度计算出的猝灭常数小.这是由于荧光强度测量中的自吸收效应引起的.实验结果表明;猝灭常数Kq与溶剂极性无关而只与粘度有关.说明这种猝灭是受扩散控制的动态猝灭.动力学分析表明,这是一种强猝灭,电荷转移猝灭速度比卟啉和醌的复合物的分解速度大或与之相近.比较实验结果和我们以前及其他作者发表的结果后,可以得出结论.苯醌对卟啉衍生物激发态电荷转移猝灭的溶剂效应随分子状态的不同而异:分子内的和通过三重态进行的分子间电荷转移猝灭受溶剂极性影响,但通过一重态进行的分子间电荷转移猝灭则与溶剂极性无关.     

Photobleaching mechanisms of Radachlorin photosensitizer in aqueous solution

The time dependence of the fluorescence intensity of aqueous solutions of Radachlorin photosensitizer at different concentrations and the influence of the dissolved oxygen concentration on the fluorescence dynamics are analyzed. The experimental results are interpreted based on the numerical solution of the system of kinetic equations describing the photochemical processes that lead to the formation and degradation of singlet oxygen in solution. The influence of possible mechanisms of photosensitizer photobleaching is analyzed. It is shown that the main photobleaching mechanism under our experimental conditions is the chemical reaction between the photosensitizer in the triplet state and dissolved oxygen molecules. Two rate constants of electron-transfer chemical reactions, which are important for understanding the nature of the occurring photoprocesses, are determined.     

Fluorescence and excited state proton transfer of pyrene-3-carboxaldehyde

In very dilute water solutions, ca 10⁻⁷ M, pyrene-3-carboxaldehyde fluoresces with a high quantum yield, øF = 0.98. This emission is quenched at low pH and, if the proton activity is high enough, a new weak, red shifted fluorescence appears. These effects are explained by the existence of a fast proton transfer in the excited state. The emitting singlet is believed to be 6–7 orders of magnitude more basic than the ground electronic state. By measuring the changes in fluorescence intensity and lifetime of pyrene-3-carboxaldehyde as a function of pH, a value for the quenching rate constant k₂ = (2.2 ± 0.3) × 10¹⁰ M⁻¹ s⁻¹ was obtained. The quenching of the neutral form fluorescence is proposed to be produced by the protonation of the excited aldehyde, followed by a fast radiationless deactivation of the conjugated acid, before prototropic equilibrium can be attained.     

Temperature dependences of dual fluorescence as criterion for determining character of photoreactions

We performed comparative studies of the temperature quenching of dual fluorescence of acetonitrile solutions of several molecular probes with proton transfer reaction in an excited singlet state of 4′-(dieth-ylamino)-3-hydroxyflavone (FET), 1-methyl-2-(4-methoxy)phenyl-3-hydroxy-4(1H)-quinolone (QMOM), and 3-hydroxyflavone (3HF) parent molecule at different energies of excitation quanta. In accordance with expressions obtained from balance equations for photoreactions of the kinetic and thermodynamic character, the intensity ratios of fluorescence bands as functions of the degree of quenching behave differently. Namely, the quenching increases the relative intensity of bands normal form/tautomer for reactions of the kinetic type, retaining this ratio unchanged for reactions of the thermodynamic character. Our experimental studies showed that, for fluorescent probes with the kinetic reaction (3HF and QMOM), the intensity ratio fluorescence bands increases almost linearly with the degree of quenching, whereas, in the thermodynamic case (FET), this ratio is independent of this parameter. Conclusions about the character of reactions that we obtained in this work agree well with data of independent investigations of these molecules by laser spectroscopy with high time resolution, and the obtained relations allow us also to judge the mechanism of temperature quenching in the case of the reaction of the kinetic type. The method can be used for comparatively simple express selection of molecular probes, candidate for new applications.     

Excitation spectrum of two correlated electrons in a lateral quantum dot with negligible Zeeman splitting

The excitation spectrum of a two-electron quantum dot is investigated by tunneling spectroscopy in conjunction with theoretical calculations. The dot made from a material with negligible Zeeman splitting has a moderate spatial anisotropy leading to a splitting of the two lowest triplet states at zero magnetic field. In addition to the well-known triplet excitation at zero magnetic field, two additional excited states are found at finite magnetic field. The lower one is identified as the second excited singlet state on the basis of an avoided crossing with the first excited singlet state at finite fields. The measured spectra are in remarkable agreement with exact-diagonalization calculations. The results prove the significance of electron correlations and suggest the formation of a state with Wigner-molecular properties at low magnetic fields.     

Mechanism for quenching of the luminescence of 9,10-anthraquinone vapor by oxygen

The fluorescence of 9,10-anthraquinone, 1-aminoanthraquinone, 1,4-diaminoanthraquinone, and 1,5-diaminoanthraquinone is not quenched by oxygen because the singlet-triplet energy difference in these compounds is less than the energy needed for excitation of the triplet state of oxygen to the singlet state. Luminescence of 9,10-anthraquinone is quenched because it is mainly phosphorescence, for which the singlet-triplet difference is sufficient for quenching by a mechanism involving singlet oxygen formation. The weak fluorescence of 9,10-anthraquinone is not quenched. The resistance of the fluorescence of 9,10-anthraquinone vapor to quenching by oxygen and the quenching of its phosphorescence explain the different effects of oxygen on the luminescence of α-substituted and β-substituted anthraquinones known from the literature, and indicate that their singlet excited state cannot convert triplet oxygen to singlet oxygen. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 79–4, January–February, 2008.     

Studying reactions that proceed from highest excited states of molecules using fluorescence quenching

The steady-state monochromatic excitation of a luminophore that has fluorescing products is considered. The effect of dynamic quenching of highest excited states on the fluorescence of singlet states under its excitation via singlet S ₁ and S _n (n ≥ 2) states is discussed. It is shown that the use of the method of fluorescence dynamic quenching by foreign impurities opens new possibilities for studying photoreactions that proceed via S _n singlet states. A large number of primary photoprocesses are considered which include the electron density redistribution (the internal electron transfer) in the excited state, protolytic reactions, intramolecular proton transfer (phototautomerization), hydrogen bonding, and formation of excimers and exciplexes. It is shown that, upon dynamic quenching, the bimolecular quenching constant of an excited level depends on the amount of thermal energy released in the luminophore before the occurrence of the light emission event. Based on the experimental measurements of the fluorescence spectra at different quencher contents, the calculation of the Stern-Volmer constant for reaction products is considered in detail. It is shown that this constant can be most reliably determined from the dependence of the fluorescence intensity ratio of the initial reagents and the quencher product rather than from the dependence of the fluorescence intensity of the products on the concentration of the quencher. The relations determined are used in analysis of the experimental fluorescence spectra of solutions of 3-hydroxyflavone excited by radiation with different wavelengths lying in the range of the S ₁ and S ₂ absorption bands. The temperature behavior of the Stern-Volmer constant for different fluorescence bands of 3-hydroxyflavone is considered. It is shown that, if these constants for the normal and tautomeric forms are correctly determined, their temperature dependences are similar.     

磁场对异质界面上D-中心的影响

势阱中的类氢杂质的能级问题一直为学术界所长期关注。讨论了异质界面上中性施主D⁰和负施主离子D^-的能量随垂直于界面的磁场的变化情况,同时将磁场和势阱结合起来考虑其对类氢杂质的影响。研究发现随磁场的增大,其对D⁰基态能的影响越来越大,对其束缚能的影响逐渐变小,而对D^-中心,磁场的作用使得D^-由非束缚态转变为束缚态。计算中分别选取了两种不同的波函数,分析了这两种波函数的适用范围,利用变分的方法得到此结构中D⁰中心的基态能量和束缚能与D^-中心角动量L=-1自旋三重态的本征能量和束缚能随磁场的变化关系,找到了此三重态由非束缚态转变到束缚态对应磁场的阈值。     

Avian magnetoreception model realized by coupling a magnetite-based mechanism with a radical-pair-based mechanism

Many animal species have been proven to use the geomagnetic field for their navigation, but the biophysical mechanism of magnetoreception has remained enigmatic. In this paper, we present a special biophysical model that consists of magnetite-based and radical-pair-based mechanisms for avian magnetoreception. The amplitude of the resultant magnetic field around the magnetic particles corresponds to the geomagnetic field direction and affects the yield of singlet/triplet state products in the radical-pair reactions. Therefore, in the proposed model, the singlet/triplet state product yields are related to the geomagnetic field information for orientational detection. The resultant magnetic fields corresponding to two materials with different magnetic properties are analyzed under different geomagnetic field directions. The results show that ferromagnetic particles in organisms can provide more significant changes in singlet state products than superparam- agnetic particles, and the period of variation for the singlet state products with an included angle in the geomagnetic field is approximately 180 when the magnetic particles are ferromagnetic materials, consistent with the experimental results obtained from the avian magnetic compass. Further, the calculated results of the singlet state products in a reception plane show that the proposed model can explain the avian magnetoreception mechanism with an inclination compass.     

Single-molecule spectroscopy of radical pairs,a theoretical treatment and experimental considerations

ABSTRACT

In this work, we propose to extend the scope of single-molecule spectroscopy to spin chemistry investigations of single radical pairs. A consistent theory of single-molecule spectroscopy on single radical pairs is proposed, which allows one to show that bunching phenomena are affected by singlet–triplet interconversion in radical pairs, which is, in turn, affected by local and external magnetic fields. A detailed study on the feasibility of such experiments with single flavin adenine dinucleotide, FAD, molecules is presented. We conclude that the observation of magnetic field effects on single FAD molecules is feasible but experimentally challenging for measurements on integrated fluorescence intensity and fluorescence event statistics.     

The influence of excitation radiation parameters on photosensitized generation of singlet oxygen in water

Photosensitized generation of singlet oxygen with the aid of Radahlorin® photosensitizer has been investigated. The dependences of the intensity of singlet oxygen phosphorescence and photosensitizer fluorescence on the excitation radiation wavelength in the range of 350–440 nm and on the irradiation dose have been obtained. The dependence of the ratio of the sensitizer fluorescence intensity at about 670 nm to the singlet oxygen phosphorescence intensity at a wavelength of 1270 nm on the excitation radiation wavelength is found to be nonmonotonic and have a minimum near the center of the absorption band on its red wing. The results obtained can be used to monitor the singlet oxygen concentration in solutions.     

Polarized nonequilibrium Bose-Einstein condensates of spinor exciton polaritons in a magnetic field

The effect of a magnetic field on a spinor exciton-polariton condensate has been investigated. A quenching of a polariton Zeeman splitting and an elliptical polarization of the condensate have been observed at low magnetic fields B<2 T. The effects are attributed to a competition between the magnetic field induced circular polarization buildup and the spin-anisotropic polariton-polariton interaction which favors a linear polarization. The sign of the circular polarization of the condensate emission at B<3 T is negative, suggesting that a dynamic condensation in the excited spin state rather than the ground spin state takes place in this magnetic field range. From about 2T on, the Zeeman splitting opens and from then on the slope of the circular polarization degree changes its sign. For magnetic fields larger than the 3 T, the upper spin state occupation is energetically suppressed and circularly polarized condensation takes place in the ground state.     

Determination of the diffusion and viscosity coefficients from the properties of dual fluorescence of molecules in solutions

We have proposed and substantiated an approach that makes it possible to determine the diffusion and microviscosity coefficients in solutions from characteristics of the dual fluorescence of molecular probes. This approach uses the Stern-Volmer constants obtained upon fluorescence dynamic quenching in solutions. The relations that follow from the balance equations in terms of the formalism of two-level reactions in the excited state for the case of photoreactions of the kinetic character yield the dependences of the intensity ratio of the fluorescence bands of the normal form and tautomer on the degree of quenching. In accordance with these dependences, the dynamic quenching of the diffusion character (including the temperature quenching) changes the intensity distribution, and, based on these dependences, the Stern-Volmer constants and the bimolecular quenching constants can be determined, from which, using appropriate models, the diffusion and viscosity coefficients can be found. The merit of the method is its simplicity and availability, since it is based on the use of the data of steady-state measurements of fluorescence spectra with widespread standard instruments.     

Magneto-vibratory separation of glass and bronze granular mixtures immersed in a paramagnetic liquid

A fluid-immersed granular mixture may spontaneously separate when subjected to vertical vibration, separation occurring when the ratio of particle inertia to fluid drag is sufficiently different between the component species of the mixture. Here, we describe how fluid-driven separation is influenced by magneto-Archimedes buoyancy, the additional buoyancy force experienced by a body immersed in a paramagnetic fluid when a strong inhomogeneous magnetic field is applied. In our experiments glass and bronze mixtures immersed in paramagnetic aqueous solutions of MnCl₂ have been subjected to sinusoidal vertical vibration. In the absence of a magnetic field the separation is similar to that observed when the interstitial fluid is water. However, at modest applied magnetic fields, magneto-Archimedes buoyancy may balance the inertia/fluid-drag separation mechanism, or it may dominate the separation process. We identify the vibratory and magnetic conditions for four granular configurations, each having distinctive granular convection. Abrupt transitions between these states occur at well-defined values of the magnetic and vibrational parameters. In order to gain insight into the dynamics of the separation process we use computer simulations based on solutions of the Navier-Stokes' equations. The simulations reproduce the experimental results revealing the important role of convection and gap formation in the stability of the different states.     

Time-resolved luminescence and singlet oxygen formation under illumination of hypericin in acetone

We present time- and spectral-resolved phosphorescence study of hypericin as well as evolution of singlet oxygen formation and elimination under the illumination of hypericin in acetone solution. The obtained time-resolved hypericin phosphorescence can be satisfactorily fitted by using a two-exponential decay curve. The value of shorter component is about 0.29 μs and is independent of the hypericin concentration in the studied range (2–200 μM). The rise time of singlet oxygen production matches this value perfectly. It confirms that singlet oxygen formation represents the significant channel of hypericin triplet state deactivation under aerobic conditions at room temperature. The total phosphorescence intensity of hypericin is linearly proportional to the hypericin concentration within the studied concentration range, but the singlet oxygen phosphorescence intensity exhibits saturation behavior. This observation is a result of at least two effects: quenching of singlet oxygen by hypericin, as well as quenching of singlet oxygen by singlet oxygen.     

Low-power green-to-blue and blue-to-UV upconversion in rigid polymer films

Green light excitation of platinum octaethylporphyrin (PtOEP) in poly(methyl methacrylate) (PMMA) films containing 9,10-diphenylanthracene (DPA) yielded emission of blue light under ambient conditions. This energy upconversion process was easily observed using low-power monochromatic excitation. The blue light emission arose from fluorescence of the lowest excited singlet state of DPA formed by spin-allowed annihilation of two DPA triplets excited by the transfer of the triplet energy from PtOEP to DPA. The upconversion emission intensity was proportional to the square of the excitation intensity, and an upconversion quantum efficiency of ∼0.0002 was measured at an excitation intensity of only 0.9 mW cm⁻². High concentrations of molecularly doped emitter facilitated triplet energy migration in rigid PMMA. Upconverted fluorescence was also observed from other emitters and with other sensitizers, including blue-to-UV upconversion in a PMMA film containing the non-heavy metal sensitizer 2-methoxythioxanthone and the emitter 2,5-diphenyloxazole.     

Magneto and Electro-Optic Intensity Modulator Based on Liquid Crystal and Magnetic Fluid Filled Photonic Crystal Fiber

We propose a novel light intensity modulator based on magnetic fluid and liquid crystal(LC) filled photonic crystal fibers(PCFs). The influences of electric and magnetic fields on the transmission intensity are theoretically and experimentally analyzed and investigated. Both the electric and magnetic fields can manipulate the molecular arrangement of LC to array a certain angle without changing the refractive index of the LC. Therefore, light loss in the PCF varies with the electric and magnetic fields whereas the peak wavelengths remain constant. The experimental results show that the transmission intensity decreases with the increase of the electric and magnetic fields. The cut-off electric field is 0.899 V/um at 20 Hz and the cut-off magnetic field is 195 m T. This simple and compacted optical modulator will have a great prospect in sensing applications.