甲醇分子(CH3OH)光谱性质的理论计算

研究了气相甲醇分子(CH3OH)基态和激发态性质。在对不同方法基组所得计算结果和实验结果进行比较之后,选用MP2(full)/6-311++G(2d,2p)理论方法进行计算,得到甲醇分子(CH3OH)基态和三重激发态的几何结构、能量以及频率信息;频率计算显示基态和三重态都为稳定构型。从三重态的结构出发,解释了三重态势能面为排斥型势能面的合理性。计算了甲醇分子单重激发态的垂直激发能,比较不同方法不同基组计算的甲醇分子单重激发态的垂直激发能,发现用TDDFT 中的b3p86方法使用6-311++G**基组的计算值和实验值符合得最好。计算得到的甲醇分子在MP2(full)/6-311++G(2d,2p)的绝热电离能和垂直电离能分别为11.18eV和11.32eV;计算得到的绝热电子亲和势与垂直电子亲和势分别为0.888eV和0.893eV。计算结果对实验研究有指导意义。     

Phase transitions of indirect excitons in coupled quantum wells: The role of disorder

The theory of what happens to a superfluid in a random field, known as the “dirty boson” problem, directly relates to a real experimental system presently under study by several groups, namely excitons in coupled semiconductor quantum wells. We consider the case of bosons in two dimensions in a random field, when the random field can be large compared to the repulsive exciton–exciton interaction energy, but is small compared to the exciton binding energy. The interaction between excitons is taken into account in the ladder approximation. The coherent potential approximation (CPA) allows us to derive the exciton Green's function for a wide range of the random field strength, and in the weak-scattering limit CPA results in the second-order Born approximation. For quasi-two-dimensional excitonic systems, the density of the superfluid component and the Kosterlitz–Thouless temperature of the superfluid phase transition are obtained, and are found to decrease as the random field increases.     

Theoretical predictions of the electronic and optical properties of single and coupled (In,Ga)As/GaAs quantum dots

We show how an atomistic pseudopotential plus many-body configuration interaction theory can address the main spectroscopic features of self-assembled dots including, excitons, trions, biexcitons, fine-structure, charging spectra as well as electric-field dependence of entanglement in dot molecules.     

Regioselective E(trans)-Z(cis) photoisomerization in naphthyldiene derivatives

Naphthyldiene derivatives,1-4, carrying electron-donating groups at one end and electron-withdrawing groups at the other, were synthesized to study the photoisomerization process. All the compounds showed efficient photoisomerization upon direct excitation leading to the formation of 4-Z isomer with high selectivity. Triplet sensitization studies indicated inefficientE-Z isomerization process. Room temperature fluorescence of1 and2 displayed fine structure in hexane solvent and the same was replaced by broad or structureless fluorescence in acetonitrile and methanol solvents. A mechanism involving a polarized or charge transfer singlet excited state is proposed for the observed photoisomerization in these naphthyldiene derivatives.     

正常金属/自旋三重态p波超导体结隧道谱的奇异性

利用Blonder，Tinkham和Klapwijk理论计算了正常金属/绝缘层/正常金属/自旋三重态的p波超导体结的隧道谱和平均电流.计算结果表明：在自旋三重态p波超导结的隧道谱中存在零偏压电导峰、零偏压电导凹陷和双凹陷结构，并有微分电导随偏压震荡的现象出现，在I-V曲线上出现电流台阶.这些结果在理论上支持Sr₂RuO₄的超导态是自旋三重态p波超导态. 关键词： 自旋三重态超导体 p波超导体 隧道谱     

利用光子统计概率测量单分子光子源的信号背景比

理论上研究了基于Hanbury Brown Twiss 探测方式，利用单光子和双光子统计概率P RS(1),PRS(2),直接测量单分子光子源的信号背景比.在研究过程中同时考 虑到单分子布居于暂稳态和探测器量子效率对测量结果的影响.在满足PRS(1)2 PRS(2)-3PRS(2)的条件时，研究给出了一种有效测量信号背景比的方 法SBR=P2RS(1)/2PRS(2).另外，分析讨论了Mandel参数Q 与信号背景比之间的关系. 关键词： 单分子光子源 信号背景比 光子统计 暂稳态 Mandel参数     

Photoinduced electron transfer in solutions of A Pd-porphyrin-quinone complex

Photoinduced electron transfer (PET) in a Pd-porphyrin-quinone complex (Pd-P-Q) was investigated using the flash photolysis method in microsecond and picosecond range and by luminescence. The investigations were performed for toluene solutions. Intramolecular PETs in the lower excited singlet state (k_CT=1.7·10¹⁰ sec⁻¹) and in the triplet state (k_CT=2.5·10⁸sec⁻¹) were observed. For a quantum yield of the triplet state that is close to 1 in Pd-porphyrin (Pd-P) this yield is equal to 0.4 in Pd-P-Q. This decrease is the result of PET in the excited state and, possibly, in an unrelaxed triplet state. Triplet Pd-P-Q molecules were efficiently quenched by unexcited molecules, and this process is related to intermolecular charge transfer. This electron transfer is likely to occur from the Pd-P protion of an excited molecule to the quinone protion of an unexcited molecule in the collisional complex (Pd-P-Q)₂. Charged radicals, formed once the collisional complex is transferred and separated, have a wide absorption band with a maximum of about 960 nm. The average lifetime of the radicals was about 2 msec. Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No 1 pp. 61–70, January–February, 1997.     

Photophysics ofβ-carotene and related compounds (review)

A review of data on the photophysics of carotenoids is presented. Results of investigations of spectroscopic, temporal, and energy parameters of excited S₁ and S₂ singlet states of β-carotene and related compounds are critically examined. These states give rise to extremely high probabilities (10¹¹–10¹³ sec⁻¹) of radiationless deactivation of the electronic excitation energy in carotenoids. Results of investigations of photophysical properties of triplet states of carotenoids are considered mainly from the standpoint of quenching of singlet oxygen and triplet states of organic molecules by carotenoids. Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 5–19, January–February, 1997.     

Regularities of triplet-triplet annihilation of aromatic hydrocarbons in aqueous micellar solutions of sodium dodecyl sulfate

Investigation of deactivation processes in triplet states of a series of aromatic hydrocarbon molecules (antracene, 1,2-benzantracene, and 3,4-benzpyrene) made it possible to reveal the presence of triplet-triplet annihilation of the molecules in aqueous micellar solutions of sodium dodecyl sulfate. It is shown that the effect of microheterogeneous solutions on the process of triplet-triplet annihilation manifests itself in an increase in the probability of excimerization upon dissociation of triplet pairs of 1,2-benzantracene and 3,4-benpyrene molecules compared to one-component solutions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 626–628, September–October, 1997.