The evaluation of temporal electronic structures of nonresonant Raman excited virtual state of thiourea

An algorithm has been introduced to calculate molecular bond polarizabilities of thiourea, which supply essential electronic information about the nonresonant Raman excited virtual states. The main dynamical behaviour of the excited virtual states of thiourea is that the Raman excited electrons tend to flow to the N-H bonds and C-N bonds from the S-C bonds because of the electronic repulsion effect. The difference in Raman excited electron relaxation time of thiourea under 514.5-nm and 325-nm excitations has been observed, which quantitatively shows that the Raman scattering process is dependent on the wavelength of the pumping laser. Finally, the distribution of the electrons at the final stage of relaxation is given out through the comparison between the bond electronic densities of the ground states and the bond polarizabilities after deexcitation.     

卟啉酞菁二元分子光谱及激发态弛豫的非简并四波混频研究

通过对卟啉酞菁二元分子TTPP-O-Pc和TTPP-O(CH_2)_5-O-Pc的发射光谱和激发光谱的系统研究,证实了(tetratolylphenyl porphyrin)TTPP到Pc的能量转移,区分了后一种材料中发射光谱的两组谱带的来源.利用非简并四波混频(NDFWM)方法研究了二元分子激发态弛豫过程,获得了这两种材料的激发态弛豫时间分别为3.6ps和4ps,以及电荷弛豫时间分别为18.5ps和82ps.     

电子的交换作用对激发态能量的影响

根据作者提出的物理模型和简洁有效的计算方法,考虑电子交换应对于激发态的影响,计算了激发态Ｌｉ原子（１ｓ＾２４ｓ）＾２Ｓ１／２的能量。计算结果表明：电子的交换能对低激发态的贡献较大,而对较高激发态（５ｓ、６ｓ…以上）在计算过程中可以忽略不计。     

Be等电子序列的奇宇称(J=2)的高激发态结构

应用本征通道量子亏损理论(EQDT),研究BeⅠ等电子序列(奇宇称,J=2)的高激发态结构,得到了表征高激发态结构的EQDT参量(U_iα,μ_α),以这些参量作为输入,获得了2snp、2pns、2snf、2pnd组态的Rydberg能级位置及通道混合系数。讨论了高激发态沿该等电子序列的变化规律。     

压强对冰Ⅶ相结构影响的拉曼光谱研究

测量了室温下2.5～23GPa压强下冰Ⅶ相的拉曼光谱。测量结果表明:随压强增加,冰的氧原子间距离dO—O减小,使氢键长度变短,导致O—H化学键键长增加,力常数减小,拉曼光谱发生红移。质子(氢核)取向有序性随压强先增加而后减小致使拉曼光谱强度先增加而后减小;拉曼光谱线宽先减小而后增加,当压强约为13GPa时呈现最小值。     

亚乙基硫脲分子激发拉曼虚态的研究

本文从拉曼峰强入手,求得了亚乙基硫脲(ETU)分子的"时间分辨键极化率",并讨论了该分子的激发拉曼虚态性质,发现了该分子"激发虚态电子向分子外围键流动"、"电子弛豫后的键极化率分布与基态电子的密度分布相似"、"不同激发波长下的键极化率衰减时间满足不确定关系"等特点。本文还研究了该分子的表面增强拉曼光谱,指出"电荷转移机制"的极化率弛豫时间长于"电磁增强机制"等与表面增强拉曼效应相关的结论。     

Chiral asymmetry of anti-symmetric coordinates studied by the Raman differential bond polarizability of S-phenylethylamine

<正>The Raman optical activity(ROA) study on 5-phenylethylamine is presented by the intensity analyses via bond polarizability and differential bond polarizability.Ample information concerning the physical picture of this chiral system is obtained,and its ROA mechanism is constructed.Especially,we propose that the asymmetric modes and/or the off-diagonal elements of the electronic polarizability tensor are the potential keys to the exploration of ROA.     

Quenching of the triplet state of tetrapyrrole molecules by Ni-, Ag-, and Fe-porphyrins and formation of excited complexes and photoproducts

Using the method of pulse photolysis, we studied the quenching of the triplet state (TS) of a number of tetrapyrrole molecules by complexes of Ni-, Ag-, and Fe-porphyrins in liquid solutions at a temperature of ∼298 K under the conditions where the kinetics are markedly affected by the triplet-triplet annihilation of the molecules of energy donors. In the analysis of experimental data, derivatives for the time dependences of the optical density of the triplet-triplet absorption were determined. The triple-triplet annihilation process was considered for the case of the formation of excited a triplet-triplet complexes of two molecules in the triplet state. A procedure of determining the rate constant for the quenching of the triplet state by foreign molecules (K_q) under the effect of such triplet-triplet annihilation process is proposed and the values of K_q are obtained. For some donor-quencher pairs it is found that the kinetics of the triplet-state deactivation are affected by the formation of short-lived particles with lifetimes both shorter and longer than the triplet-state lifetimes. The conclusion is drawn that such particles are respectively the excited complexes of interacting molecules or ion radicals formed from such complexes in polar solvents. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 3, pp. 296–300, May–June, 2000.     

Calculation of the vibronic spectra and structure of methylstyrene in the excited state by the parametric method

Calculations of the excited-state structure and of the absorption and radiation spectra of trans-β-methylstyrene are performed by the parametric method for models of the first and second approximations. Only three of the parameters, being constant in a series of related compounds, are used for molecular fragments. In the calculation, the main regularities observed in electronic spectra are reproduced, and an analysis and interpretation of their fine vibrational structure are carried out. The use of the model of the second approximation with a single additional parameter allows more accurate reproduction of angular deformations of the molecule under excitation and of the characteristic changes observed in the low-frequency spectral region in the series of diphenyl polyenes, stilbene, styrene, and methylstyrene molecules. It is shown that the parameters of the second approximation (just as of the first one) possess the transference property in the homological series of molecules. In modeling complex molecules in excited states and their vibronic spectra, the parametric method is more efficient than the ab initio one. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 148–153, March–April, 2000.     

Preparing of coherent superposition state in serial multi-A-type system by stimulated Raman adiabatic passage

A scheme for creating an arbitrary coherent superposition of two atomic states in serial multi-A-type system is proposed.This technique with the application of a control field is based on the existence of two degenerate dark states and their interaction.The mixing of the dark states can be controlled by changing the relative delay time of the control pulse.One can get any desired superposition by changing the delay time of the control pulse.