等离子体X射线吸收谱及发射谱研究

 报道计算高温高密等离子体吸收谱和发射谱（光学薄）的理论方法；该方法基于相对论原子理论，可以计算任何单元素以及多元素等离子体的谱分辨X射线吸收谱和发射谱（光学薄）；应用了量子亏损理论，可以减少计算量。利用该方法计算金等离子体LTE吸收谱，计算结果与实验符合良好。本文还对金等离子体LTE的光学薄发射谱进行了研究, 这将有利于对实验进行进一步的诊断分析。该理论计算方法还可提供等离子体内各电离度能级布居等重要物理参数。因此经“标准实验”检验的该理论计算方法将是提供ICF“精密”物理辐射参数的重要基础。     

等离子体X射线吸收谱及发射谱研究

报道计算高温高密等离子体吸收谱和发射谱（光学薄）的理论方法;该方法基于相对论原子理论,可以计算任何单元素以及多元素等离子体的谱分辨X射线吸收谱和发射谱（光学薄）;应用了量子亏损理论,可以减少计算量。利用该方法计算金等离子体LTE吸收谱,计算结果与实验符合良好。本文还对金等离子体LTE的光学薄发射谱进行了研究, 这将有利于对实验进行进一步的诊断分析。该理论计算方法还可提供等离子体内各电离度能级布居等重要物理参数。因此经“标准实验”检验的该理论计算方法将是提供ICF“精密”物理辐射参数的重要基础。     

MOC染料单分子层薄膜聚集体的吸收光谱研究

用吸收光谱对染料的Langmuir-Blodgett(LB)膜的聚集体在不同条件下进行了研究.典型的染料1-methyl-1’-octadecy1-2,2’-cyaninperchlorate(MOC)LB膜聚集体的吸收峰(J带)在580nm附近,吸收为0.09.刚制备好的样品随时间而改变其吸收特性,表明聚集体的结构在2hr后才趋于稳定;测定了不同样品J带的参数;吸收峰值波长位置和峰的半宽度,以及这些参数随温度的变化.吸收随温度变化的可逆性是LB膜聚集体用作光记录介质的一个物理基础.温度超过100℃时,样品吸收的不可逆变化反映相变发生.     

IR absorption and surface-enhanced Raman spectra of the isoquinoline alkaloid berberine

We present the IR absorption and surface-enhanced Raman scattering (SERS) spectra of the isoquinoline alkaloid berberine adsorbed on a silver hydrosol and on the surface of a silver electrode for different potentials. Based on quantum chemical calculations, for the first time we have assigned the vibrations in the berberine molecule according to vibrational mode. The effect of the potential of the silver electrode on the geometry of sorption of the molecule on the surface is considered, assuming a short-range mechanism for enhancement of Raman scattering. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 31–36, January–February, 2007.     

Theoretical analysis of the experimental UV-Vis absorption spectra of some phenolic Schiff bases

The time-dependent density functional theory (TDDFT) was applied in conjunction with the natural bond orbital analysis to examine the UV-Vis properties of 10 phenolic Schiff bases. The calculations were performed with different functionals, but main discussion refers to results obtained at the B3LYP/6-311+G(d,p) level of theory. The approach based on the natural localised molecular orbital clusters indicates similar behaviour for majority of examined compounds. The HOMO (“highest occupied molecular orbital”) cluster is delocalised over the ring which is electron richer, the HOMO-1 cluster is spread over the other ring, whereas the LUMO (“lowest unoccupied molecular orbital”) cluster is situated on the imino group. The two bands at long wavelengths correspond to the HOMO → LUMO and HOMO-1 → LUMO transitions, i.e. from both A and B rings to the imino group. The next band originates from a transition from the imino group to the imino group. The band at the smallest wavelengths originates from a transition from the A ring to the A ring, or from the B ring to the B ring. Our findings are in very good agreement with the existing literature data.     

Analysis of interaction between the organic dye methylene blue and the surface of AgCl(I) microcrystals

We have used IR spectroscopy to study the nature of interaction between molecules of the organic dye methylene blue (MB) and the surface of AgCl(I) microcrystals. We recorded the IR absorption spectra of the organic dye methylene blue in the gas phase, adsorbed on the surface of AgCl(I) microcrystals, and also in the form of crystal hydrates. The results obtained allowed us to hypothesize that unsaturated dimethylamino groups and the sulfur atom in the heterocycle of this dye are the most active in the interaction between methylene blue molecules and the surface of AgCl(I) microcrystals. With the help of IR spectra of methylene blue crystal hydrates, we confirmed the significant role of OH groups during adsorption of molecules on the surface of AgCl(I) microcrystals. We suggest the possibility of formation of hydrogen bonds between the anions of the crystal lattice and the unsaturated dimethylamino groups as well as the sulfur atoms in the heterocycle, by formation of hydrogen bonds with the OH groups. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 731–737, November–December, 2007.     

低对称畸变晶场下YIG和YGG:Fe~(3+)吸收光谱的理论解释

本文利用络合物中Fe~(3+)的SCF-d轨道理论,分别在实际的低对称场D_(3d)和S_4下对YIG和YGG:Fe~(3+)中的d-d跃迁谱进行了理论计算。仅用两个参数和μ就解释了YIG中10800cm~(-1),21150cm~(-1),25700cm~(-1),27600cm~(-1)处的谱分裂,并且指出YGG:Fe~(3+)中的26320cm~(-1),26970cm~(-1)为Fe~(3+)对的双中心跃迁谱。基本澄清了YIG和YGG:Fe~(3+)吸收谱理论的某些混淆。     

有机染料HEASPS在不同波长时的激发态吸收和双光子吸收性质研究

提出了有机染料反式 4 [4′ (N 羟乙基 N 乙基胺基 )苯乙烯基 ] N 甲基吡啶对甲苯磺酸盐 (简称HEASPS)非线性吸收的三态模型。认为在较短波长 (<1 0 0 0nm)时 ,双光子吸收和激发态吸收同时存在。成功地解释了该染料双光子吸收峰相对线性吸收峰的两倍的明显蓝移 ,以及最高上转换效率波长相对最强吸收波长的明显红移。提出了一种新的计算方法 ,利用不同波长的非线性透过率和不同波长的上转换效率 ,求出了该染料的双光子吸收截面和激发态吸收系数。     

Electron absorption spectra of univalent copper-, silver-, and gold-thiourea complexes in aqueous solutions

Using data on the stability of complex forms, electron absorption spectra of copper (I)-, silver (I)-, and gold (I)—thiourea complexes in an aqueous solution M_itu_j (Ag: i=1, 2, j=1–3; Cu: j=1, 2; Au: j=2) are calculated from the spectra of solutions of a known analytical composition. Parameters of particular bands of the absorption spectra of these complexes are given. It is found that the integral intensity of the spectra of the solutions is proportional to the concentration of thiourea in the solution with high accuracy. The same is also valid for the spectra in solutions that contain mercury (II) and thiourea. The total intensity of longwave bands in the spectra of the complexes is proportional to the number of ligands in a molecule of the complex. Institute of Ionorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3, Lavrent’ev Ave., 630090, Novosibirsk-90, Russia, Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 458–462, July–August, 1997.     

Two-photon absorption and nonlinear optical properties of a new organic dye PSPI

Trans-4-[p-(pyrrolidinyl)styryl]-N-methylpyridinium iodide (abbreviated as PSPI thereafter) is a two-photon absorption (TPA) dye newly synthesized by our research group. It possesses much larger TPA cross-section and much stronger upconversion fluorescence emission than those of common organic dye (such as rhodamine) when excited with near infrared (IR) radiation. TPA spectrum and upconversion efficiency spectrum of HEASPI solution at various wavelengths were measured. There is 34 nm blue shift for the central wavelength of the TPA induced absorption peak compared with two times of the linear absorption peak. The biggest molecular TPA cross-section σ₂^′ is 2.85×10⁻⁴⁷ cm⁴ s/photon at 930 nm. At 1064 nm, σ₂^′ is 3.12×10⁻⁴⁸ cm⁴ s/photon. The highest efficiency is 3.9% at 1010 nm, whereas 2.9% at 1064 nm. Its optical power limiting properties at 930 nm have also been illustrated.     

Quasiline fluorescence and absorption spectra of NH-isomers of octamethylisobacteriochlorin

Quasiline fluoresence and fluorescence excitation spectra of NH-isomers of 2,2,7,7,12,13,17,18-octamethylisobacteriochlorin (cis- and trans-) in polycrystalline matrices in n-hexane and n-octane at 4.2 K are obtained. A vibration analysis of the spectra in combination with the data of quasiline spectra of cyano-substituted octaethylisobacteriochlorin and octamethylporphin permitted a qualitative interpretation of the vibronic spectra of NH-isomers. It is inferred that for a trans-isomer, the 0–0 transition S₂⇃S₀ is localized in the region of electron-vibrational S₁⇃S₀ transitions; the interval S₂-S₁ has a magnitude of about 1300 cm⁻¹. Reported at the VIIIth International Conference on the Spectroscopy and Chemsitry of Poprhyrins and Their Analogs, Belarus, Minsk, September 22–26, 1998. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 79–85, January–February, 2000.     

A theoretical investigation on the electronic structures and phosphorescent properties of three heteroleptic iridium(III) complexes with different substituted ancillary groups

Three heteroleptic iridium(III) complexes 1, 2 and 3 bearing two cyclometalating 2′,6′-difluoro-2,3′-bipyridyl (dfpypy) chelates and one pyridyl pyrazolate ligand have been investigated by using the density functional theory/time-dependent density functional theory method to study the influence of the different substituent groups (―CF₃ and ―N(CH₃)₂ moiety on the electronic structures, phosphorescent properties and the organic light-emitting diode performance. The lowest energy absorption wavelength calculated is in good agreement with the experimental value. The lowest energy emissions of complexes 1, 2 and 3 are localised at 454, 534 and 821 nm, respectively. Ionisation potential and electron affinity have been calculated to evaluate the injection abilities of holes and electrons into these complexes. The calculated results show that the different substitute groups affect the charge transfer rate and balance. Finally, we hope that this study can provide a good guide to the future design and synthesis of novel phosphorescent materials for use in the organic light-emitting diodes.     

染料敏化太阳能电池光敏剂卟啉儿茶酚的密度泛函和含时密度泛函研究

用密度泛函理论的杂化密度泛函B3LYP方法研究了太阳能电池光敏荆5,10,15.三苯基-20-(3,4-二羟基苯)卟啉(卟啉儿荼酚,TPP-cat)的几何结构、电子结构、IR和Raman特性.用自然键轨道方法分析了电荷布居和成键性质.计算结果表明,最强的IR吸收峰位于1175.81 cm-1处,最强的Raman活性位于1587.18 cm-1处.采用含时密度泛函计算了TPP-cat在水溶液中的电子吸收谱,其Soret带和Q带均指认为π→π*跃迁,在大约354 cm-1处的跃迁与一个光诱导分子内电荷转移过程有关.     

Ab initio calculations for the absorption spectra and polarizabilities of small sulfur clusters

Absorption spectra for Sn clusters （n=2...8） are calculated using an adiabatic time-dependent density functional formalism within the local density approximation （LDA）. We compare the calculated spectra with those computed using a simple LDA approach. The time-dependent LDA （TDLDA） spectra display a significant blue shift with respect to the LDA spectra. The calculated spectra present a variety of features that can be used for comparison with future experimental investigations. We also obtain a significant threshold absorption, which can distinguish between different ground states of the sulfur clusters. In addition, the polarizabilities of the clusters are calculated by using the higherorder finite-difference pseudopotential density functional method in real space. We find that the polarizabilities of the clusters considered are higher than the value estimated from the ＇hard sphere＇ model using the bulk static dielectric constant. The computed polarizabilities per atom tend to decrease with increasing cluster size. The polarizabilities are closely related to the HOMO-LUMO gaps and the geometrical configurations.     

Co,Zn共掺铌酸锂电子结构和吸收光谱的第一性原理研究

利用基于密度泛函的第一性原理的计算方法,研究了Co单掺及Co和Zn共掺LiNbO_3晶体的电子结构和吸收光谱.研究显示,各掺杂体系铌酸锂晶体的带隙均较纯铌酸锂晶体变窄. Co:LiNbO_3晶体禁带宽度为3.32 eV; Co:Zn:LiNbO_3晶体, Zn的浓度低于阈值或达到阈值时,禁带宽度分别为2.87或2.75 eV. Co:LiNbO_3晶体在可见-近红外光波段2.40, 1.58, 1.10 eV处形成吸收峰,这些峰归结于Co 3d分裂轨道的跃迁;加入抗光折变离子Zn~(2+),在1.58, 1.10 eV处的吸收峰增强,可以认为Zn~(2+)与Co~(2+)之间存在电荷转移,使e_g轨道电子减少,但并不影响t_(2g)轨道电子.结果表明,晶体中的Co离子在不同共掺离子下可充当深能级中心(2.40 eV),或可充当浅能级中心(1.58 eV),两种情况下,掺入近阈值的Zn离子均有助于实现优化存储.     

Plasma emission spectra of working media of KrC1 and XeC1 electric-discharge lasers

Results of investigations of survey spectra of plasma emission of the working media of inert-gas-chloride electric-discharge lasers in the 200–600 nm range are reported. In the UV spectra, FeI lines, which are of interest for lasing with optical pumping of iron vapors by excimer molecules, were observed. In the visible spectrum, a number of HeI, KrI, and XeII lines are suggested for determination of electron density and investigation of the discharge instability on XeCl^* and KrCl^* molecules. Uzhgorod State University, 46, Pidgirna St., Uzhgorod, 294000, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 523–527, July–August, 1997.     

一种新型有机染料HEASPS在不同波长时的双光子吸收和频率上转换性质研究

报道了一种新型双光子吸收染料 ,即反式 - 4- [4′- (N-羟乙基 - N-乙基胺基 )苯乙烯基 ]- N-甲基吡啶对甲苯磺酸盐的非线性光学性质 ;测试了染料在 72 0～ 110 0 nm波段的非线性透过率曲线。结果发现 :双光子吸收最强波长相对线性吸收峰波长的两倍处有明显蓝移 ;计算出的相应波长的双光子吸收截面在 930 nm处染料有最大双光子吸收截面(2 .0 6× 10 - 4 7cm4·s/ photon) ;测量了染料在 90 0～ 110 0 nm波段的上转换效率 ,在 10 2 0 nm处有最高效率 (5 .1% ) ,最高激射效率的波长相对最强双光子吸收的波长有明显红移     

Signature of the hydrogen-bonded environment of liquid water in X-ray emission spectra from first-principles calculations

Based on ab initio molecular dynamics simulations and density functional theory, we performed a systematic theoretical study to elucidate the correlation between the H-bonded environment and Xray emission spectra of liquid water. The spectra generated from excited water molecules embedded in an intact H-bonded environment yield broader spectral peaks and a larger spectral range than the spectra generated from water molecules in a broken H-bonded environment. Such differences are caused by the local electronic structures on the excited water molecules within the core-hole lifetime that evolve differently through the rearrangement of neighboring water molecules in different H-bonded environments.     

Effects of light quenching on the emission spectra and intensity decays of fluorophore mixtures

We examined a series of fluorophore mixtures to determine the wavelength selectivity of light quenching and the effects of light quenching on the emission spectra and intensity decays. Light quenching can be accomplished using a single excitation pulse train and quenching wavelength (one-beam) or with longer-wavelength quenching pulses time-delayed relative to the excitation pulses (two-beam). Both one-beam and two-beam light quenching were found to alter the intensity decays of the mixtures. The frequency-domain intensity decay data were analyzed to reveal the fractional intensity of each fluorophore in the mixture and the effects of light quenching on the fractional contribution of each fluorophore to the total intensity. Fluorophores were selected to provide a range of decay times and emission wavelengths. The extent of quenching in the mixtures was dependent on which fluorophore had the higher radiative decay rate and emission intensity at the quenching wavelength. A general theory is presented which describes the intensity decays in terms of the extent of quenching of each fluorophore and the time delay between excitation and quenching pulses. The effects of light quenching on the fractional intensities of each fluorophore in the mixture, recovered from the intensity decay analysis, were found to be in quantitative agreement with that predicted from steady-state measurements of light quenching and from the spectral properties of the fluorophores. The data on light quenching of mixtures demonstrate that light quenching may be used for selective quenching of fluorophores and thus of potential value for studies of multichromophoric systems.