First-order distributed feedback dye laser effect in reflection pumping geometry

Tunable distributed feedback lasing output based on reflection grating configuration instead of the traditional transmission one was realized from rhodamine 6G (R6G)-doped ethanol and 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl)-4H-pyran-(DCM)-doped methanol. Pure gain coupling and additional index coupling were obtained in R6G-doped ethanol and DCM-doped methanol, respectively. The tuning, which was found to be independent of the refractive index of the lasing media, went through the entire stimulated emission band for the two cases. Dual-peak lasing emission indicative of the existence of an index grating was observed in DCM-doped methanol. The interval between the two peaks increased with pump energy.     

番茄红素的紫外可见光谱和荧光光谱分析

研究了番茄红素在不同溶剂中的紫外可见光谱图,对结果进行分析后发现番茄红素在正己烷、石油醚、丙酮、乙酸乙酯具有较低折光率的溶剂中的特征吸收带波长非常接近,但在较高折光率的溶剂苯、二硫化碳中的特征吸收带与以丙酮作为溶剂相比有不同程度的红移。番茄红素溶于丙酮与水的混合溶剂,当丙酮与水的体积比达到3∶2时,吸收光谱在紫外区出现一新的吸收峰,在可见区吸收光谱的精细结构消失。用荧光光度计采集不同溶液的番茄红素的荧光光谱,番茄红素的荧光峰位于580—590nm,在极性溶剂中荧光发射增强。     

基于溶剂化效应的BDE-15分子振动光谱增强特征振动研究

利用密度泛函与自洽反应场理论在B3LYP/6-31+G(d)水平下分别计算气态及24种不同极性溶剂中4,4’-二溴二苯醚(4,4’-dibrominated diphenyl ethers, BDE-15)的分子振动光谱(红外光谱、拉曼光谱),以气态分子振动光谱为基准,筛选出对溶剂极性敏感的特征振动作为指标构建溶剂对BDE-15振动光谱溶剂化效应指标体系,探究溶剂对BDE-15分子振动频率、红外/拉曼峰强溶剂化效应及综合效应,并寻求显著增强BDE-15分子特征振动频移/强度的溶剂。研究表明：从分子振动频率角度,溶剂极性敏感的(频移>1 cm-1)分子特征振动均为伸缩振和面外弯曲振,但24种溶剂对BDE-15分子振动频率溶剂化效应并不显著;从分子振动峰强角度,24种溶剂对BDE-15分子振动光谱峰强的增强效应主要发生在红外光谱的中低频区及拉曼光谱的高频区,其中起显著增强(红外/拉曼效应指标值分别大于6与5)的溶剂为醇类、乙腈、二甲亚砜、硝基苯;不同极性溶剂对BDE-15拉曼峰强溶剂化效应及综合效应指标值均表现出随溶剂介电常数增长由线性到对数的增长趋势,而红外峰强只保留低介电常数溶剂时的线性关系。利用上述BDE-15分子振动光谱峰强增强方法对BDE-153,BDE-154和BDE-209进行验证,醇类、乙腈、二甲亚砜、硝基苯对三者的振动光谱红外/拉曼峰强的效应指标值分别大于6与5,且最大峰强增倍数皆大于33,说明所建BDE-15分子振动光谱增强特征振动方法有助于进一步开展基于分子振动光谱的PBDEs同系物间辨识研究。     

Solvent Effects on the Electronic Absorption Spectra of Cr(III) Complexes

An influence of the protic solvents on the electronic absorption spectra of chromium (III) complexes was investigated. The high correlation between dielectric constant of solvents and the crystal field parameter Dq as well as between refractive index and oscillator strength of d-d bands were observed. The significance of the ligand - second sphere interactions for studying of solvent effect on complex spectra was stated.     

若丹明6G溶液体系的荧光量子效率

本文对八种若丹明6G溶液的荧光量子效率进行了测量,并着重讨论了染料若丹明6G溶液体系的量子效率的溶剂效应.在研究中发现:若丹明6G溶渡的荧光量子效率与溶液极性(ε-1)/(2ε+1)之间存在线性关系,体系的荧光量子效率随溶剂极性的增加而下降.由于染料分子与成氢键溶剂作用愈强,能量散逸愈快将是导致这一结果的主要原因.这一规律也适用于ANS染料溶液体系中.     

溶剂对香豆素343染料光谱性质和最低激发态偶极矩的影响

通过对香豆素343(C343)在不同溶剂中的稳态吸收光谱、稳态荧光光谱和时间分辨荧光光谱的分析,研究了溶剂对C343的光谱性质的影响,并获得了光谱特性与溶剂极性之间的依赖关系. 吸收光谱峰值的红移随着溶剂极性的增加而发生较小的变化. 然而,荧光光谱的峰值对溶剂的极性却很敏感,并随着溶剂极性参数f(ε,n)的增加呈线性增长. 这是由于C343激发态电荷分布的变化导致了它在极性溶剂中第一激发单重态能级的变化. 用溶剂效应测量法和量子化学计算方法确定了C343最低激发态的偶极矩,这两方法所得的结果一致. C343在不同溶剂中的时间分辨荧光光谱研究表明荧光寿命随着溶剂极性的增加而增加,即从甲苯溶液的3.09 ns线性地增加到水溶液中4.45 ns;荧光寿命延长的根源可归因于C343与氢键给体溶剂之间的分子间氢键相互作用.     

Specific effects of a polar solvent in optical absorption spectra of 1,2-naphthoquinone

The optical absorption spectra of 1,2-naphthoquinone in polar (methanol) and nonpolar (n-hexane) solvents are recorded. It is found that the specific effect of a polar solvent, which manifests itself in a hypsochromic shift of the first nπ* band and in a bathochromic shift of the second and third ππ* bands, is caused by the formation of hydrogen bonds between solvent molecules and the molecule under study and, as a result, by a change in the energy gap between the corresponding occupied and unoccupied molecular orbitals. This result is obtained by TDDFT B3LYP/6-311+G(d, p) calculations of electronic spectra, which, in the case of an isolated 1,2-naphthoquinone molecule, reproduce its experimental optical absorption spectra in n-hexane and, in the case of the same molecule forming a complex with methanol molecules by means of hydrogen bonds, reproduce the spectrum of 1,2-naphthoquinone in methanol.     

饱和一元醇远红外光谱的测试及仿真研究

用衰减全反射傅里叶光谱仪(FTIR-ATR)在室温条件下测试了甲醇、乙醇、丙醇、异丙醇、丁醇及异丁醇六种饱和一元醇在30～300 cm-1波段的远红外透射光谱。通过分析这六种具有类似化学结构的一元醇的远红外透射光谱,发现它们在30～150 cm-1波段均有明显的吸收峰,但在150～300 cm-1波段吸收峰不明显; 羟基在一元醇中的质量百分比越高,相关一元醇的远红外光谱的平均透过率越低; 直链一元醇的光谱平均透过率高于支链状的同分异构体。采用密度泛函理论B3LYP/6-311G(d,p)基组对甲醇单体和多聚体进行结构优化和频率计算。计算显示,在30～150 cm-1波段甲醇单体分子没有出现吸收峰,但是甲醇的多聚体则出现明显的吸收峰,计算得到的多聚体吸收峰位置与实际测量的结果相符合。结果表明,甲醇在太赫兹波段吸收的来自于不同形式聚合体的集体振动,甲醇溶液以甲醇三聚体为主要的存在形式。本成果不仅为研究有机分子在太赫兹波段的频率响应提供了新的实验方法,而且对进一步利用FTIR-ATR研究其他有机分子具有借鉴意义。     

A New Candidate Laser Dye Based 1,4-Bis[β-(2-Naphthothiazolyle)Vinyl]Benzene. Spectroscopic Behavior,Laser Parameters and Excitation Energy Transfer

A new candidate laser dye based 1,4-bis[β-(2-naphthothisolyl) vinyl] benzene (BNTVB) were prepared, and characterized in various organic solvents. The center polarity is less sensitive than electronic absorption. A red shift was noticed in the fluorescence spectra (ca. 40 nm) with increment in the solvent’s polarity, this means that BNTVB’s polarity appreciates upon excitation. The dipole moment of ground state (μ_g) and the excited singlet state dipole moment (μ_e) are determined from Kawski – Chamma and Bakshiev–Viallet equations using the disparity of Stokes shift with solvent polarity function of ε (dielectric constant) and n (refractive index) of the solvent. The result was found to be 0.019D and 5.13D for ground and exited state, in succession. DFT/TD-DFT manners were used to understand the electronic structures and geometric of BNTVB in other solvents. The experimental and theoretical results showed a good agreement. The photochemical quantum yield (Ф_c) of BNTVB was calculated in variable organic reagents such as Dioxane, CHCl₃, EtOH and MeOH at room temperature. The values of φ_c were calculated as 2.3?×?10^?4, 3.3?×?10^?3, 9.7?×?10^?5 and 6.2?×?10^?5 in Dioxane, CHCl₃, EtOH and MeOH, respectively. The dye solutions (2?×?10^?4 M) in DMF, MeOH and EtOH give laser emission in the blue-green region. The green zone is excited by nitrogen pulse 337.1 nm. The tuning range, gain coefficient (α) and cross – section emission (σ_e) of laser were also estimated. Excitation energy transfer from BNTVB to rhodamine-6G (R6G) and N,N-bis(2,6-dimethyphenyl)-3,4:9,10-perylenebis-(dicarboximide) (BDP) was also studied in EtOH to increase the laser emission output from R6G and BDP when excited by nitrogen laser. The dye-transfer power laser system (ETDL) obeys the Foster Power Transmission (FERT) mechanism with a critical transmission distance, R_o of 40 and 32 ? and k_ET equals 2.6?×?10¹³ and 1.06?×?10¹³ M^?1 s^?1 for BNTVB / R6G and BNTVB / BDP pair, respectively.     

Mechanisms of specific effects of polar solvent in optical absorption spectra

We measured the optical absorption spectra of para-benzoquinone and duroquinone in polar (methanol) and nonpolar (n-hexane) solvents. We find that the specific effect of the polar solvent, which manifests itself here as a bathochromic shift of one of π-π* bands, is caused by the formation of hydrogen bonds between solvent molecules and the molecule under study and, as a consequence, by a decrease in the energy gap between the corresponding occupied (π) and unoccupied (π*) molecular orbitals. This result is obtained by TDDFT B3LYP/6-311+G(d, p)-calculations of electronic spectra, which, in the case of isolated para-benzoquinone and duroquinone molecules, reproduce experimental optical absorption spectra of the corresponding compounds in n-hexane and, in the case where these molecules form complexes with methanol molecules by means of hydrogen bonds, reproduce spectra measured in methanol.     

Theoretical calculations on the NaS and NaS+ radicals: electronic structure, spectroscopy and spin-orbit couplings

We propose a closed three-level V-type system with an incoherent pumping which achieves a high index of refraction without absorption via spontaneously generated coherence. The system has two near-degenerate excited levels. We derive full analytical formulas for the index of refraction and the gain (absorption) coefficient. We found that the proper choice of the incoherent pumping, the relative phase of the two coherent fields, the Rabi frequencies, the probe detuning and the angle between the two transitions leads to the enhancement of the refractive index without absorption.     

Influence of the Bulk and Donor-Acceptor Properties of Solvent on Ligand Field Spectra

The influence of solvents on the electronic absorption spectra of chromium (III) complexes was investigated. The dependence of the crystal field parameter Dq on dielectric constant as well as Gutmann donor number DN of solvent was found and described. By using the proposed model, unknown in the literature donor numbers for a few alcohols were estimated.     

双酚酸的合成及其紫外光谱研究

利用乙酰丙酸和苯酚缩合反应制取双酚酸（DPA）,并采用红外光谱及核磁光谱对其结构进行了表征。研究了DPA在水、乙腈、甲醇和环己烷4种溶剂中的紫外光谱。结果发现,在这4种溶剂中,DPA溶液的紫外光谱主要在210nm左右及260nm左右有两个强吸收峰。210nm左右的吸收峰对溶剂的极性及溶液的浓度敏感。而260nm左右的吸收峰在各种极性不同的溶剂中的位置变化不明显,对溶液浓度也不敏感。因此,DPA在260nm吸收峰可以用于DPA的定量分析,而210nm吸收峰可用于研究DPA与其他分子的相互作用。另外,溶剂极性对两个吸收峰强度的影响也不相同。     

两种新香豆素分子的热力学和光谱性质

使用密度泛函理论方法在B3LYP /6-31++G**理论水平对两种香豆素a和b分子的几何结构、光谱、热力学性质进行理论计算研究,并基于Tomasi的极化统一场模型(PCM)讨论溶剂效应。结果显示,香豆素a和b分子在气相中的最低能量吸收波长分别为352和355 nm,溶剂及其极性大小对香豆素a最低能量吸收波长影响很小,但在溶剂作用下香豆素b分子的最低能量吸收波长红移7-10 nm,溶剂的极性对该波长影响较小。298 K标准压力下香豆素a和b分子的气态标准摩尔生成焓 分别为-1373.171和-1310.805 kJ.mol-1,标准摩尔生成自由能 分别为-1064.043和-1035.849 kJ.mol-1,标准摩尔熵 分别为763.910和742.150 J.mol-1.K-1.     

Photosensitivity and photoluminescence of Sn/Yb codoped silica optical fiber preform

Sn/Yb codoped silica optical fiber preform is prepared by the modified chemical vapor deposition （MCVD） followed by the solution-doping method. Ultraviolet （UV） optical absorption, photoluminescence （PL） spectra under 978-nm laser diode （LD） pumping, and refractive index change after exposure to 266-nm laser pulses are obtained. There is only a little change in the PL spectra while a positive refractive index change up to 2×10^-4 is observed after 30-min exposure to 266-nm laser pulses. The results show that both of the peculiar photosensitivity of Smdoped silica and the gain property of Yb-doped silica fiber are preserved in the Sn/Yb codoped silica optical fiber preform. The experimental data suggest that the photosensitivity of the fiber preform under high energy density laser irradiation should be mainly due to the bond-breaking of oxygen deficient defects, while under relatively low energy density laser irradiation, the refractive index change probably originates from the photoconversion of optically active defects.     

UV-spectral changes for some azo compounds in the presence of different solvents

The electronic absorption spectra of four azo dyes with different substituents (such as Cl, I, OH) are determined at room temperature in twenty-one solvents with different polarities. The electronic transitions of azo dyes are interpreted. Linear solvation energy relationships have been investigated for solvatochromic behaviors and solute-solvent interactions of azo dyes. Linear solvation energy relationships were performed by multiple linear regression analysis using dielectric function, refractive index function and Kamlet-Taft parameters. We have observed that the hydrogen bonding acceptor ability and the induction-dispersive forces of solvent molecules have caused the bathochromic shift in absorption maxima of azo dyes.     

双丙酮丙烯酰胺的紫外光谱研究

双丙酮丙烯酰胺（DAAM）是一种应用广泛的聚合物单体,可与其他乙烯基单体共聚得到性能各异的聚合物材料,而对DAAM的光谱研究报道较少。文章主要研究了DAAM在水、乙腈、甲醇和环己烷四种溶剂中的紫外光谱。结果发现,在这四种溶剂中,DAAM溶液的紫外光谱主要在200 nm左右及226 nm左右有2个强吸收峰。200 nm左右的吸收峰对溶剂的极性及溶液的浓度非常敏感。在极性溶剂中200 nm吸收峰发生蓝移,在极性较大的乙腈及水中,蓝移更大;在各种溶剂中,200 nm吸收峰都随溶液浓度增大而发生红移。而226 nm左右的吸收峰在各种极性不同的溶剂中吸收峰的位置变化不明显,对溶液浓度也不敏感。因此,DAAM在226 nm吸收峰可以用于DAAM的定量分析,而200 nm吸收峰可用于研究DAAM与其他分子的相互作用。另外,溶剂极性对2个吸收峰强度的影响也不相同。     

光纤回音壁模式的三波段激光辐射研究

将石英光纤浸入低折射率的激光染料溶液中构成圆柱形微腔.采用沿光纤轴向光抽运的消逝波激励增益方式,获得了沿光纤轴向长距离的激光染料增益,受激辐射光在圆柱形微腔中回音壁模式的支持下形成激光振荡.在直径为288 μm的同一根光纤外分三段分别填入罗丹明6G、罗丹明610和罗丹明640激光染料乙二醇溶液,实现了波长分别在567～575 nm、605～614 nm和656～666 nm三个不同波段的回音壁模式激光振荡,用一根光纤同时获得了红、橙、黄三种不同颜色的激光辐射.对实验所获得的回音壁模式激光光谱做了模式标定,依据标定的模式数计算了各种模式以及抽运光在光纤截面的强度分布.计算结果表明,激光增益区域总是局限在圆柱形微腔回音壁模式的模场区域内,由此可以显著地提高抽运效率,增加抽运光沿光纤轴向的增益长度.     

脱氢枞酸基D-A型分子的合成、空间构型及光谱性能

对三苯胺进行溴代和C-N偶联反应合成4-萘基三苯胺(a),对脱氢枞酸进行酯化、溴代、硝化、还原和C-N偶联反应合成13-[N,N-(4-萘基苯基)-苯基]胺基-脱异丙基脱氢枞酸甲酯(b)及13-[N,N-双(4-萘基苯基)]胺基-脱异丙基脱氢枞酸甲酯(c)两个化合物,通过1H MNR,13C MNR及MS对化合物的结构进行表征。为了研究化合物结构与光谱性能之间的关系,首先利用Gaussian 09程序采用密度泛函DFT/B3LYP方法,对三个化合物的空间构型进行全优化,得到它们的键长、键角和二面角,对比发现脱氢枞酸骨架和萘环的引入会影响化合物的共平面性,而萘环的引入会增大化合物的共轭程度。光谱性能方面,研究了三种化合物在甲醇、二氧六环、四氢呋喃、二氯甲烷和环己烷这5种极性逐渐减小的溶剂中的荧光发射光谱和紫外吸收光谱。结果表明,在荧光光谱中,化合物a,b和c在不同极性溶剂中最大荧光发射波长均有不同程度位移,在甲醇中最大,在环己烷中最小,但是位移并非随着极性的增大而只发生红移,在二氯甲烷、四氢呋喃和二氧六环3种极性依次增大的溶剂中,a,b,c的荧光发射波长均随着溶剂极性的增大而发生较大程度的蓝移;在同一溶剂中,化合物b和c相对于a的荧光发射波长依次发生红移,c的红移程度与b差距不大。紫外吸收光谱中,三个化合物在不同极性溶剂中的最大吸收波长也有差异,在200～250 nm区间,三个化合物均在二氯甲烷中有较大位移,在300～350 nm区间,在甲醇中位移较大,而在250～300 nm区间,最大吸收波长差别不大;在同一溶剂中,它们在300～350 nm区间的最大吸收波长差别较大,化合物c较a红移26 nm。结合结构优化所得数据可以证明,化合物的共轭程度对荧光发射光谱和紫外吸收光谱均有影响,而共平面性对荧光发射光谱影响较大。化合物a,b和c在不同极性溶剂中荧光发射光谱和紫外吸收光谱的较大变化,表明它们有明显的溶致变色行为,具有作为分子探针探测外部环境极性大小的潜能。     

Solvent Dependence on Structure and Electronic Properties of 7-(Diethylamino) - 2H -1- Benzopyran-2- one (C-466) Laser Dye

In this work, we studied influences on the absorption and fluorescence emission spectra of coumarin-4066 (C-466) with different solvent polarity scale. The spectral shifts reflect the effect of the equilibrium solvents association across the energized solute particle, which adjusts inertially as a result of quick charge realignment upon radiative deactivation to the lowest electronic state. The dipole moments of C-466 are determined by employing the Bakhshiev, Kawski-Chamma-Viallet, Lippert-Mataga and McRae relations. The results from all these methods are, excited state dipole moment of C-466 is higher than the ground state dipole moments and which indicates molecule is less polar in the ground state. Theoretical analysis was also carried out by Density Functional theory (DFT and TD –DFT) employing the BECKE-1998 (exchange)/STO-6G basic set in ethanol solvent and in vacuum medium. The HOMO-LUMO, Solvent Accessible Surfaces (SAS) and Molecular Electrostatic Potential (MEP) were analysed to acquire additional knowledge of the molecular arrangement and electronic properties of C-466. These photophysical properties suggest delineation can be mauled for laying out new luminescent tests for various solvents microenvironment.