NO2分子内能传递和弛豫过程的光声和荧光光谱探测

将荧光光谱和光声光谱两种互补的探测技术结合起来,从辐射和无辐射跃迁两个方面,分析了 532nm激光作用下,NO2分子的激发和弛豫过程.发现NO2分子在激光作用下,将跃迁至第一激发电子态.当样品气压较低时,受激NO2分子除辐射荧光外,可通过快速的内能转移过程实现在几个振转能级的再布居;随样品气压的升高,分子间碰撞加剧,受激NO2分子通过分子间的碰撞,实现在多个振转能级的再布居.激光布居能级的荧光辐射效率随样品气压的升高逐渐降低,而长波区域的荧光辐射及光声信号强度逐渐增强,说明在高样品气压条件下,受激NO2分子的弛豫过程除辐射荧光外,还存在很强的碰撞弛豫过程,在碰撞弛豫过程中受激NO2分子将振动能转化为热运动的平动能,引起温度升高而产生很强的声信号.     

Solvatochromic and Fluorescence Behavior of Sulfisoxazole

The Fluorescence spectroscopic and solvatochromic behavior of Sulfisoxazole, a sulfa drug with antimicrobial activities, in various pure solvents of different polarity and hydrogen bonding capability is reported. The fluorescence emission spectrum of sulfisoxazole was found to be solvent polarity dependent, where a notable red shift in emission maximum was observed with increasing solvent polarity as well as hydrogen bonding capability. The effects of the latter two solvent parameters were quantitatively investigated using the methods of Lippert–Mataga and solvatochromic comparison method (SCM) that is based on the Kamlet-Taft equation. Particularly, the Lippert–Mataga method was applied to estimate the dipole moment of the excited state (μ_e) upon plotting Stokes shift versus solvent polarizability (Δf), where a value of 11.54 Debye was obtained. On the other hand, applying the multiple regression analysis to the SCM method revealed that solvent polarizability (π*) and hydrogen-bond donor capability (α) approximately equally stabilize sulfisoxazole in the excited state with minor destabilization contribution by the hydrogen-bond acceptor capability (β). These findings revealed that the excited state of sulfisoxazole is stabilized by polar solvents, indicating that this drug molecules exhibit larger dipole moment in the excited state than in the ground state, which in turn implies that a potential intramolecular charge transfer (ICT) occurs after excitation.     

乙醛紫外多光子电离动力学研究

本文报道了在分子束条件下,用XeCl准分子激光多光子电离乙醛的质谱研究结果。碎片离子强度与进气量之间的线性变化关系表明乙醛的多光子电离(MPI)过程是一个单体反应,揭示了乙醛紫外光解的一些性质。由取得的质谱、质谱中碎片离子强度与激光光强之间的变化关系,以及其乙醛第一单重激发态¹(n,π^*)的光物理性质,我们提出了母体分子离解——中性碎片电离模型,根据这个模型,可以解释实验结果。 关键词：     

Lifetime-measurements of alkali-molecules excited by different laserlines

Absorbing different lines of acw-argon ion laser or a He-Ne-laser the alkali molecules Na₂, K₂, Rb₂ and Cs₂ can be pumped into different rotational-vibrational levels of an excited electronic state. The lifetimes of these states have been measured using the phase shift technique at a modulation frequency of 18 Mc/sec. Because of collisions with the always present alkali atoms the excited molecules may undergo collision-induced transitions to other states and their lifetimes are dependent on the atomic pressure. This dependence was measured and the spontaneous lifetimes were obtained by extrapolation against zero pressure. Different collision processes are discussed which compete with the unperturbed fluorescence.     

Relaxation effects in the ESR of Gd in the metallic Van-Vleck paramagnet: PrSb

The ESR g shift and linewidth of Gd in the metallic Van-Vleck paramagnet, PrSb, exhibit appreciable change upon increasing the temperatures above T = 20 K. A model is suggested to explain the linewidth behavior. It is argued that while the g shift behavior is mainly associated with the admixture of the first excited crystalline field level, Γ₄, into the singlet ground state Γ₁, the relaxation is primarily via the Γ₅ excited state of Pr³⁺     

有机材料激子发光的温度特性

基于实验和理论模拟研究了12~320 K温度范围内八羟基喹啉铝[tris-(8-hydroxyquinoline)aluminum,Alq]和一种高效红光染料甲基2叔丁基6(1,1,7,7四甲基久咯呢定基9烯基)4H 1吡喃[4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran,DCJTB]的光致发光(photoluminescence,PL)随温度的变化,提出三种不同电荷分离程度的激子参与的Alq的稳态光致发光过程,通过拟合参量得到了三种激子的能量差值和辐射复合几率之比,观察并解释了DCJTB发光光谱从200 K以下到室温的升温过程中发生的蓝移。认为变温光致发光有可能用于评估材料的发光和导电性能,比较并讨论了有机和无机发光材料激子发光的温度特性,认为低温下小分子发光材料倾向于分子态,随温度升高逐渐向半导体态转变,Alq在150~190K之间开始发生这种转变,而DCJTB则从300~320 K开始。     

High pressure electrical transport behavior in organic semiconductor pentacene

The high pressure electrical transport behavior of pentacene has been investigated by alternating current impedance techniques and direct current resistivity measurement in a diamond anvil cell (DAC). The resistance decreases with increasing pressure below 17.4?GPa, while it increases above 17.4?GPa, which is caused by the transition of pentacene from an ordered state to the disordered state under higher pressure. From the Raman spectra under various pressures, pentacene becomes amorphous above 17.3?GPa, which is consistent with the impedance results. The charge transport operates in the hopping regime with charges jumping between interacting molecules, and the hopping mechanisms are related to the vibration modes. Above 17.4?GPa, the pressure dependence of the relaxation activation energy is 21.7?meV/GPa and pentacene keeps semiconductor characteristics up to 28.3?GPa.     

A search for mechanoluminophors capable of pressure-induced thermal population of excited states

During the process of deforming a crystal, a high pressure is developed near the tip of mobile cracks, which may in turn produce a new ground state by thermal electron transfer. Upon sudden release of pressure, the electron can either relax to one atmosphere ground state or remain in the excited state potential well long enough to relax to one atmosphere and radiatively transfer back to the ground state. For analysing the pressure induced thermal population of the excited state, the mechanoluminescence(ML) and high pressure photoluminescence(PL) of several organic and inorganic crystals were measured. The study indicated that usual pressure coefficient of energy shift of the order of 50–100 cm⁻¹/kbar and the stress at the crack-tip of the order of 5–10 kbar, are not sufficient to cause the thermal population of the excited state. If by any means the product of pressure coefficient and stress at the mobile crack-tip can be increased by 50 to 100 times, then the thermal population of the excited states may take place. Using the pressure coefficient of energy shift and the difference in ML and PL spectra, and using independently the change in relative intensities of the vibronic peaks, the pressure at the emitting mechanoluminescent crystal sites is evaluated and it is found to be of the order of several kbar which varies from crystal to crystal.     

A Modification of Förster's Deactivation Relation due to Inhomogeneous Spatial Distribution and Active Behavior of the Acceptors

The deactivation behavior of excited molecules and impurities in solids is analyzed under consideration of a long-range excitation energy transfer based on dipole-dipole interaction between donors and acceptors. Under the condition of inhomogeneous spatial distribution and active behavior of the acceptors a time evolution formula is derived, which essentially differs from Förster's original relation [2]. The results are discussed for physically representative values of concentration and medium parameters.     

Excited state intramolecular proton transfer of 1,2-dihydroxyanthraquinone by femtosecond transient absorption spectroscopy

1,2-Dihydroxyanthraquinone (alizarin) shows dual emission bands with a large Stokes shift from a “locally-excited (LE)” and “proton-transferred (PT)” tautomers in the excited state. Excited state intramolecular proton transfer (ESIPT) reaction of alizarin is tunable by changing concentration, solvent polarity, excitation wavelength, and etc. ESIPT reaction of alizarin in the excited state was investigated by steady-state absorption/emission spectroscopy and femtosecond transient absorption spectroscopy. In ethanol solution, the lifetime of PT tautomer of alizarin was measured as 87 ps, in addition to 0.35 and 8.3 ps vibrational cooling dynamics for the LE and PT tautomers of alizarin, respectively. In binary mixtures of ethanol and water, the excited state dynamics became more complicated; the LE and PT tautomers appeared to decay with 8.9 and 30.8 ps lifetimes, which is much shorter compared to the lifetime of the PT tautomer in ethanol. A long-lived nonradiative state in the excited states of alizarin was found as well, which was proposed as a “trapped” state with tightly hydrogen-bonded water molecules. The ESIPT reaction of alizarin was blocked in a 1:1 mixture of ethanol-water due to strong hydrogen bonding between water molecules and alizarin, which was further confirmed by the efficient coupling of alizarin to TiO₂ nanoparticles in the 1:1 binary mixture of ethanol-water.     

Red Emitting Coumarin—Azo Dyes : Synthesis,Characterization, Linear and Non-linear Optical Properties-Experimental and Computational Approach

The coumarin molecules with 7-(N,N-diethylamino) substitution and aryl azo (Ar–N=N-) at 3-position were synthesized, by reacting diazonium salt of substituted amines and 7-(N, N-diethylamino)-4-hydroxy coumarin under basic conditions. They were found to be fluorescent despite the presence of azo group. The azo group rotation was blocked by complexing with -BF₂, so as to get a red shift in absorption. The azo molecules show charge transfer, whereas BF₂-complexes do not. The dipole moment ratios between the ground and excited states calculated suggest highly polar excited state and an intra-molecular charge transfer at the excited state in the case of azo dyes. The NLO properties were calculated by solvatochromic method and computationally. Second order hyperpolarizability was found to be 46 to 1083 times more than urea. DFT and TDTDF calculations were performed to understand the electronic properties of the molecules at the ground as well as excited states.     

激发态下甘氨酸与水分子间氢键性质研究

在生物体中氨基酸通常以水作为溶剂,是形成细胞的重要成分.在该环境下,分子间氢键的产生会对氨基酸分子与水分子的结构和性质产生影响.为了研究其在基态和激发态下的性质,本文利用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)对甘氨酸分子和H₂O分子在基态和激发态下的分子间氢键的静电势、键长、自然键轨道(NBO)电荷、分子中的原子理论(AIM)分析、Wiberg键级b、红外(IR)光谱、空穴-电子轨道和基态与激发态之间的电子转移进行了理论研究.结果表明：分子间氢键的形成会导致分子结构的改变和红外光谱振动频率的移动.在激发态下,分子间氢键有不同程度的增强或减弱.该计算结果为氢键的形成和激发态下分子间氢键的研究提供理论依据.     

Inhomogeneous spectral broadening and the decay kinetics of the luminescence spectra of prodan

The selectively excited steady-state luminescence spectra, as well as the decay time characteristics of the luminescence, of prodan in polar solvents excited by picosecond radiation are studied. The steady-state luminescence spectra exhibit a strong inhomogeneous broadening, which is the most pronounced at elevated solution viscosities. The temporal characteristics of the luminescence decay in different spectral ranges and the instantaneous spectra suggest the presence of relaxation processes resulting in a long-wavelength shift of the emission spectrum during the lifetime of the excited state. A relation between the relaxation shift of the emission spectrum and the intermolecular orientational relaxation of solvate molecules is established.     

通过绝热过程制备W态

提出一种方案制备W态,方案基于暗态绝热过程.制备过程中,所有原子都处于基态,光纤模保持在真空态,在一定条件下可以忽略腔场激发,因此,方案非常抗消相干.方案的另一个优点是:只要满足绝热条件,不必要精确调节相互作用时间.方案成功的几率随原子数的增加而增加.     

通过绝热过程制备W态

提出一种方案制备W态,方案基于暗态绝热过程。制备过程中,所有原子都处于基态,光纤模保持在真空态,在一定条件下可以忽略腔场激发,因此,方案非常抗消相干。方案的另一个优点是：只要满足绝热条件,不必要精确调节相互作用时间。方案成功的几率随原子数的增加而增加。     

Hydrostatic pressure and magnetic field effect on the excited states in inverse parabolic quantum dot

The hydrostatic pressure (P) influence of the degenerate energy states inside an inverse parabolic quantum dot (IPQD), with and without an external magnetic field, was performed within the frame of the effective mass approximation. Our theoretical results showed that the effect of relatively high pressure clearly appeared to induce a crossing between the excited states in the strong confinement region. But in the weak confinement region, such crossing disappeared and, in addition, the excited states got reordered. In the presence of an external magnetic field the hydrostatic pressure modified the crossing points of the degenerate states. We investigated the electron-heavy hole transition energy. It displayed a blue shift with increasing the pressure values and the magnetic field strength. But it showed an adhesive red shift by increasing the IPQD size.     

Temporal dependences of dipole moments of prodan molecules

The fluorescence spectra of 6-propyl-2-dimethylaminonaphtalene (prodan), 1-(phenylamino)naphthalene (1-PAN), and 3-aminophthalimide are measured in glycerol with a picosecond resolution. The instantaneous fluorescence spectra and the correlation functions of the time-dependent Stokes shift of the fluorescence spectra of the two latter probes are used to find the time dependence of the dielectric response function of glycerol, which is necessary for calculating the charge transfer kinetics in prodan molecules. Based on the solvatochromism theory and using the experimental dependences of the time-dependent shift of the fluorescence bands for prodan molecules, which are characterized by efficient charge transfer in the excited electronic state, the kinetics of the electric dipole moment of the first singlet state is calculated.     

Frequency shift of dye laser emission in the linear approximation

The frequency shift of dye laser emission has been calculated for a wide range of Stokes shift, temperature, and populations of excited and ground state molecules. The calculated frequencies are in reasonable agreement with the experimental results.     

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.     

Solvatochromic study of three indoloquinoline derivatives: Effect of chloro group/s on the photophysics of thecompounds

Photophysical modulations of three indoloquinoline derivatives, viz., 5-Methyl-5H-indolo[3,2-c]quinoline (MIQ), 8-Chloro-5-methyl-5H-indolo[3,2-c]quinoline (CMIQ), and 2,8-Dichloro-5-methyl-5H-indolo[3,2-c]quinoline (DCMIQ) have been studied. These compounds belong to the cryptosanguinolentine family and are known to have potential anti-cancer abilities. In the present work we studied the effect of solvent polarity on introduction of one or two chloro (-Cl) group/s at chosen sites on the parent cryptosanguinolentine. The compounds exist mainly in two forms, neutral and zwitterionic, in equilibrium at ground state. Interestingly, all the three compounds exhibit hypsochromic shift in their absorption and fluorescence spectra with increase in relative permittivity of solvents in most of the cases. Blue-shift in fluoroscence might be due to lesser dipole moment of the species in the excited state. Time-resolved fluorescence spectroscopy clearly indicates the presence of two species in all the solvents in the excited state (except MIQ in water). The shift in the molecular polarity with chloro substitution/s seems to be responsible for the contributions of the two species in the excited state. The relative contributions are found to alter remarkably in a regular manner when MIQ is compared with CMIQ and DCMIQ. This behavior is supposed to be mainly due to dipole-dipole interaction between the solvent molecules and the fluorophores.