Temperature Dependence of the Efficiency of Collisional Transfer of Vibrational Energy in Mixtures of Vibrationally Excited Triplet Molecules with Foreign Gases

By the pressure dependences of the decay rates of delayed fluorescence activated by vibrational excitation of triplet molecules of benzophenone and anthraquinone, the efficiencies of collisional transfer of vibrational energy (V–V-transfer) in the vibrational quasi-continuum of the triplet state have been estimated. It is shown that the efficiencies of the process in mixtures with foreign gases increase with increasing dipole moment and polarizability of colliding molecules. In the temperature range 433–513 K, we obtained an inverse temperature dependence of the V–V-transfer efficiency, which is satisfactorily described by empirical relations taking into account long-range attractive forces. The results obtained point to the determining role of long-range attractive forces in quasi-resonance V–V-transfer of vibrational energy by molecules excited in vibrational quasi-continuum.     

Direct Measurement of Collisional Energy Transfer Between Highly Vibrationally Excited Triplet Fluorenone and Bath Gases

Intensities and decay rates of CO₂-laser induced delayed fluorescence are used to probe collisional relaxation of vibrationally excited fluorenone diluted with bath gases: He, N₂, Kr. The average energies 〈ΔE〉 transferred per collision are found to vary with vibrational energy, the energy dependences of the collisional efficiency eventually level off.     

Collisional Energy Transfer from Vibrationally Excited Polyatomic Molecules

Abstract

Intensities and decay rates of delayed fluorescence initiated by CO₂ laser excitation of the triplet-state molecules are used to probe collisional relaxation of vibrationally excited polyatomic molecules. Collisional efficiencies for large polyatomic molecules are found not to exceed the value of 10^?2-10^?3 even in most favourable case of vibrational energy exchange in collisions between parent molecules. At intermediate levels of excitation (1500—12000 cm^?1) the average energies <ΔE> transferred per collision with polyatomic molecules increase as vib>^rn, where m≥2, and decrease with increasing numbers of atoms in the excited molecules.     

Collisional Energy Transfer of Highly Vibrationally Excited Polyatomic Molecules. The Effect of Excited Molecule Complexity

Collisional relaxation was probed by CO₂ laser activated delayed fluorescence. The experimental information was adopted to determine the average energies transferred per collision (ΔE) from highly vibrationally excited polyatomic molecules to parent collider. The values of (ΔE) decreased with increasing the number of atoms in the excited molecules in line: biacetyl, acetophenone, benzophenone, antraquinone. The dependences of (ΔE) on the number of factors such as: 1) the average vibrational energy residing in the vibrational modes of excited molecules; 2) the potential of intermolecular interaction; 3) the reduced mass, and others were analyzed in details. The general interplay was noticed between (ΔE) and the molecular parameters which determined the increasing interaction strength and the decreasing energy transfer efficiency due to the adiabatic constraints on the energy transfer.     

激光感生碰撞能量转移实验

首次观察到Eu(6s6p)^P9/2至Sr(5s10s)^1So、准稳态翼为紫翼的激光感生碰撞能量转移实验现象,其荧光波长为458.42nm,峰值转移激光波长为459.75nm,并对其激发函数谱随温度和随转移激光能量改变进行实验研究,测量了激光感生碰撞能量转移谱的截面,证实了激光感生碰撞能量转移谱为非对称谱。     

Intermolecular Vibrational Relaxation in Mixtures of Excited Benzophenone and Anthraquinone Molecules with Water Vapor

The intermolecular vibrational energy transfer from triplet molecules of benzophenone and anthraquinone to H₂O molecules has been investigated. To determine the rates of establishment of vibrational (V-V) and thermal (V-T) equilibrium in a vibrational quasi-continuum of mixed singlet-triplet levels, the dependences of the decay rates and intensities of the fast and slow components of delayed fluorescence on the H₂O vapor pressure have been investigated. For V-V relaxation, the efficiencies ₁ and the mean energies E transferred per collision in mixtures with H₂O and other polyatomic foreign gases have been compared. It has been established that the efficiencies ₁ for quasi-resonant vibrational energy transfer (V-V) from benzophenone and anthraquinone to H₂O are an order of magnitude lower than the gas-kinetic ones and lower than those obtained under the same experimental conditions for such foreign gases as C₅H₁₂, SF₆, and CCl₄, and decrease with increasing temperature in the 433–513 K range. It has been concluded that the mechanism of V-V relaxation in mixtures with H₂O are determined by long-range attractive forces. In mixtures with H₂O, no acceleration of V-T relaxation due to the formation of hydrogen bonds has been revealed. The low-efficiency thermalization process (V-T relaxation) is controlled by short-range repulsive forces, and the differences between the intensities ₂ for mixtures of benzophenone and anthraquinone with H₂O and other polyatomic gases are determined by the change in the reduced mass of interacting molecules.     

Nature of the Electron Excited States and Energy Transfer in Bichromophore Coumarin Molecules

Results of experimental and theoretical research for three bichromophore molecules, trans-stilbene-CH₂-coumarin 120 (I), 4-methylumbelliferone-CH₂-UC 17, and 4-(3-fluoro)-methylumbelliferone-CH₂-UC 17 (II, III), are presented. Schemes of photophysical processes in the bichromophore molecules based on quantum chemical calculations by the INDO method and theory of radiationless transitions in polyatomic organic molecules are suggested. After optical excitation to the strong donor absorption band, the fast internal conversion processes develop there. As a result, the molecule is found in the S ₁ ^* -state localized on the acceptor moiety. It is shown that a mechanism of intramolecular transfer energy in bichromophores different from that proposed by Förster may be realized. Excitation energy, initially located on D, will be transferred from the donor moiety to the acceptor chromophore in convenience of the internal conversion process. The intramolecular electronic energy transfer from energy donor to energy acceptor may be interpreted as the internal conversion process. The rate constants of internal conversion are calculated.     

高激发态钠原子与分子碰撞能量转移及分子扩散带辐射的增强效应研究

在钠原子分子混合体系中 ,实验研究了加入缓冲气体对高位态原子分子碰撞能量转移和分子扩散带辐射的增强效应 ;运用瞬态碰撞模型作了理论计算 ,理论结果与实验结果相符合     

弱场中Ba-Sr系统激光感生碰撞过程的理论研究

针对四能级理论模型的第二种极限情况 ,提出了 Ba- Sr激光感生碰撞能量转移系统 ,该系统满足 |ω2 1| |ω4 3|。利用四能级理论模型对该 Ba- Sr系统进行了数值计算 ,并与三能级近似理论模型的计算结果进行了比较。通过比较四能级理论与三能级近似理论模型的计算结果 ,进一步证实了当 |ω2 1| |ω4 3|时 ,四能级理论模型可以过渡为三能级理论模型     

Influence of the Microstructure of Polymer Gels on the Electron-Excitation Energy Transfer Between Organic Molecules

The electron-excitation energy transfer (EEET) between ionic dyes in polyelectrolyte-network polymers with a different space distribution of charged segments has been investigated. It has been established that the structure of network polymers influences the efficiency of the EEET in them mainly due to the formation of a fractal distribution of interacting molecules. It is shown that the efficiency of the EEET can be controlled by changing the number and arrangement of charged segments of polyelectrolyte networks.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 181–185, March–April, 2005.     

Pr,Yb:ZBLAN上转换发光过程中的能量传递

详细地研究了Ｐｒ３＋，Ｙｂ３＋ＺＢＬＡＮ玻璃中Ｐｒ３＋和Ｙｂ３＋离子之间的能量传递过程、及能量传递对上转换发光的影响。实验结果表明，在９６０ｎｍ激光泵浦下Ｙｂ３＋通过Ｙｂ３＋—Ｐｒ３＋之间的交叉弛豫向Ｐｒ３＋传递能量。具体的能量传递形式有三种。Ｙｂ３＋作为敏化剂可提高Ｐｒ３＋的上转换发光强度。从Ｐｒ３＋向Ｙｂ３＋的反向能量传递过程也是存在的，具体的过程和Ｐｒ３＋向Ｙｂ３＋传递的相反。Ｐｒ３＋—Ｙｂ３＋的能量传递导致Ｐｒ３＋发光的淬灭，使Ｐｒ３＋上转换发光随着Ｙｂ３＋浓度增加出现饱和。和３Ｐ０能级相比较，Ｙｂ３＋对Ｐｒ３＋离子的１Ｄ２能级发光的淬灭作用更强     

Lie Algebraic Approach to Energy Transfer for Collinear Collision of Two Anharmonic Diatomic Molecules

An anharmonic oscillator algebra model is used to study the collinear collisions of two diatomic molecules. The transition probability for vibration-vibration energy transfer is presented. For an application of the method, we talk about the collision of N2＋CO, N2＋O2, and N2＋N2. Through long time averaging, the transition probability changes to the function of total energy of the system. Comparing the results with the quantum results, we can see that the dynamical Lie algebraic method is useful for describing the anharmonie diatomic molecular collision.     

Luminescence and Energy Transfer in Frozen Solutions of Uranyl Sulfate in Selective Excitation

Luminescence spectra of vitrified solutions of uranyl sulfate in a concentrated sulfuric acid are investigated in the range 4.2–80 K in selective laser excitation. It is shown that the luminescence spectra are a superposition of two components — the component that is related to the resonance excitation of uranyl complexes and the component that is caused by the luminescence of uranyl complexes sensitized by the transfer of electron-excitation energy from the resonance-excited centers. The nonselective character is established for the spectral migration of electron-excitation energy with participation of the bending vibrations of the uranyl complex that ensure direct vibrational transitions between neighboring electronic energy levels. The temperature evolution of the luminescence spectra can be described within the framework of the model of configuration coordinates with allowance for only the linear terms of vibronic interaction.     

激发态Cs2和H2的电子-振转能级的碰撞转移

利用相干反斯托克斯拉曼光谱(CARS)探测技术, 研究了激发态Cs2与H2间的电子-振转能级的碰撞转移。用波长为532 nm和中心波长为716 nm的两束激光同时聚焦到样品池中, 扫描CARS谱确认了H2分子的S支(△v =1, △J=2)仅在v=1, J=4,5及v=2, J=3,4能级上有布居, 用n1、n2、n3、n4分别表示(2,4)、(2,3)、(1,4)及(1,5)上的粒子数密度。从CARS线的峰值得到n2/n1、n3/n1、n4/n1分别为6.34±1.27、3.66±0.73和1.45±0.29。转移能配置到振动、转动和平动的比例分别为0.44、0.06和0.50, 能量主要分配在振动和平动上。在T=523 K和PH2=2.5×103 Pa条件下, 通过求解速率方程组和对时间分辨CARS线轮廓的分析, 得到碰撞转移速率系数k1=(6.0±1.2)×10-14 cm-3s-1和k2=(4.0±0.8)×10-13cm-3 s-1。     

近共振传能放热对氧碘化学激光器性能的影响

在氧碘化学激光器(COIL)中,O2(1Δ)与I的近共振传能反应是一个放热反应;它与水汽等的猝灭放热反应一样会对激射过程产生不利影响,而且是不可避免的。计算了猝灭放热效应对光腔气动特性输出功率的影响。得到了近共振传能放热的大小与粒子数反转和激射的光子数相关,即与光腔内的增益、光场强度分布成正比,故主要发生在激光器的上游区前半部分。模型计算表明,其影响程度大致相当于7%水汽所致的对氧碘化学激光器的影响。完善了氧碘化学激光器理论计算模型。     

基于合作能量传递的Sm~(2+)离子上转换发光

报道了Sm~(2+)离子的上转换发光。在实验上证明了变价镧系离子同样可以作为上转换材料的发光中心。在近红外光的激发下,复合Ba FCl_(0.5)Br_(0.5)∶1%Sm~(2+)-Ca F_2∶1%Yb~(3+)化合物发出红色上转换发光。上转换发射光谱中位于631,644,665,689,704,729 nm的特征发射分别来自于样品中Sm~(2+)的~5D_i(i=0,1)→~7F_j(j=0,1,2)特征跃迁。根据动力学分析及光子数拟合的结果,我们将二价Sm离子的上转换过程归因于合作能量传递,即:两个同时被激发的Yb~(3+)离子合作将能量传递给一个Sm~(2+)离子。     

Competition Between Energy Transfer and Deactivation During Quenching of Tryptophan Fluorescence of Albumin by Dye Molecules

Using quenching of Trp fluorescence by different dyes, bound to bovine serum albumin, it is shown that the spectral overlap between emission and absorption spectra does not necessarily lead to energy transfer as the sole quenching mechanism. A correlation of the limiting quenching value with the Förster overlap integral was not observed. The energy transfer efficiency was less than the quenching efficiency because of competitive radiationless deactivation processes induced by dye binding.     

Eu2+在磷酸镧中的发光及Ce3+→Eu2+的能量传递

采用高温固相反应合成了LaPO₄:Eu²⁺和LaPO₄:Ce³⁺,Eu²⁺样品,报道了Eu²⁺在LaPO₄中的发光性质和Ce³⁺→Eu²⁺的能量传递现象。文中探讨了Ce³⁺→Eu²⁺的能量传递机理,根据Dexter电多极相互作用的理论证明其为偶极子偶极子相互作用的共振能量传递。     

Electronic Excitation Energy Transfer between Different Types of Dye Molecules in a Porous Glass Matrix

The processes of electronic excitation energy transfer (EEET) between different types of dye molecules inserted into the matrix of a porous glass have been investigated. An extreme character of the dependence of the EEET efficiency on the size of pores has been revealed. The dependence of the fractal dimensionality of the distribution of dye molecules on the sizes of the pores has been determined. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 446–449, July–August, 2005.     

Calculation of laser induced collisional energy transfer in the Sr-Ca system

Based on the four-state model of laser-induced collisional energy transfer,the cross section of the collisional energy transfer in the Sr-Ca system is obtained.Various factors,including field intensity,relative speed,and temperature,which influence the collisional cross section,are discussed for illustrating the features of the Sr-Ca laser-induced collisional energy transfer(LICET) process.The calculated results show that the LICET spectral profiles obviously become narrower when the laser field intensity i...