Vibrational relaxation dynamics in transient grating spectroscopy studied by rate equations based on time-dependent correlation function

A modified model, a set of rate equations based on time-dependent correlation function, is used to study vibrational relaxation dynamics in transient grating spectroscopy. The dephasing, the population dynamics, and the vibrational coherence concerning two vibrational states are observed respectively in organic dye IR780 perchlorate molecules doped polyvinyl alcohol matrix. The result shows that in addition to the information concerning system-environment interac- tion and vibrational coherence, the vibrational energy transfer can be described by this modified model.     

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.     

Photoinduced electron transfer of Rhodamine 6G/N,N-diethylaniline revealed by multiplex transient grating and transient absorption spectroscopies

The dynamics and spectroscopic characteristics of the ultrafast photoinduced electron transfer (ET) of Rhodamine 6G (Rh6G⁺) in N,N-diethylaniline (DEA) were studied using femtosecond time-resolved multiplex transient grating and transient absorption spectroscopies. The ultrafast photoinduced forward ET from DEA to the Rh6G⁺* cation radical excited state has a time constant of τ _FET = 219–318 fs. The much slower backward ET from the neutral radical Rh6G^· to DEA⁺ with a time constant of τ _BET = 22.76–42.31 ps occurs in the inverted region. Intramolecular vibrational relaxation of the excited state takes place in τ _IVR = 2.18–6.91 ps.     

基于电子顺磁共振的ZnTPP激发态及其TEMPO各向异性的研究

为了研究卟啉类敏化剂的光致激发态能量转移和电子转移问题,本文基于紫外可见光谱仪和电子顺磁共振波谱仪,构建了以锌卟啉为研究对象的"锌卟啉-稳态自由基-二甲苯"实验体系.锌卟啉的紫外可见光谱显示,在可见光谱的B带和Q带出现明显的特征峰,是锌卟啉分子中电子由基态能级跃迁至激发态能级产生的.低温条件下受紫外可见光辐照的实验体系的电子顺磁共振波谱,检测到了稳态自由基四甲基哌啶氧化物的增强吸收电子顺磁共振波谱.根据分子激发态相关理论、光化学物理反应理论和化学诱导电子自旋极化理论对实验结果进行了分析,结果表明,四甲基哌啶氧化物稳态自由基电子顺磁共振波谱的增强吸收对应于锌卟啉光致激发态的能量转移和电子转移;四甲基哌啶氧化物在低温(143 K)下的电子顺磁共振波谱表现出的各向异性特征现象来源于氮氧自由基电子与氮核的各向异性超精细相互作用.     

瞬态自旋光栅系统的建设及其在自旋输运研究中的应用

简要介绍了瞬态光栅系统原理及光路的建设,包括瞬态光栅的产生与探测.采用了外差探测法（heterodyne detection）,大大提高了信噪比.利用瞬态自旋光栅系统,研究了(110)方向生长的本征GaAs/AlGaAs单量子阱中自旋输运特性,测得室温下电子自旋的扩散常数D_s=551 cm/s. 关键词： 瞬态自旋光栅 自旋扩散 自旋输运 自旋弛豫     

Investigating material trends and lattice relaxation effects for understanding electron transfer phenomena in rare-earth-doped optical materials

Rare-earth-doped insulators and semiconductors play an important role in a wide range of modern optical technologies. Knowledge of the relative energies of rare-earth ions’ localized electronic states and the band states of the host crystal is important for understanding the properties of these materials and for determining the potential material performance in specific applications such as lasers, phosphors, and optical signal processing. Current understanding of the systematic variations of electron binding energies in these materials is reviewed with analysis of how lattice relaxation affects the results obtained from different experimental techniques. Detailed examples are presented for rare-earth-doped YAG and LaF₃ material systems. A method for predicting the chemical shift of the 4f electrons of rare-earth impurities from the host crystal’s photoemission spectrum is also demonstrated. Furthermore, a simple model is presented that predicts host-dependent trends in the binding energies of the rare-earth ion states in materials ranging from the elemental metals to the ionic fluorides. By understanding the systematic changes in the relative energies for different states, different ions, and different host materials, insight is gained into electron transfer transitions, valence stability, and luminescence quenching that can accelerate the development of materials for optical applications.     

Experimental and theoretical evidence for the chemical mechanism in SERRS of rhodamine 6G adsorbed on colloidal silver excited at 1064 nm

The evidence for the existence of a chemical mechanism in surface‐enhanced resonance Raman scattering (SERRS) of rhodamine 6G (R6G) adsorbed on colloidal silver excited at 1064 nm is reported on the basis of experimental and theoretical analyses. A weak absorption peak at around 1060 nm for R6G‐functionalized silver nanoparticles was observed, which is not present in the individual spectra of R6G or silver nanoparticles. Theoretically, the charge difference density reveals that this weak absorption is a metal‐to‐molecule charge transfer excited state. Copyright © 2010 John Wiley & Sons, Ltd.     

InGaN薄膜中电子自旋偏振弛豫的时间分辨吸收光谱研究

采用飞秒时间分辨圆偏振光抽运-探测光谱对In_01Ga_09N薄膜的电子自旋注入和弛豫进行了研究.获得初始自旋偏振度约为02,此结果支持在圆偏振光激发下,重、轻空穴带的跃迁强度比为3∶1,而不支持1∶1或1∶094的观点同时获得自旋偏振弛豫时间为490±70ps,定性分析了自旋弛豫机理,认为BAP机理是电子自旋弛豫的主要机理. 关键词： 电子自旋 InGaN 自旋极化 自旋弛豫     

Excited states, relaxation processes, and coordination reactions in the active centers of heme proteins

Based on the results of studying hemoglobin and myoglobin molecules using the methods of laser absorption spectroscopy of superhigh time resolution, we described photophysical and spectral properties of excited states, and intramolecular electronic and thermal relaxation processes. A mechanisms of the photodissociation reaction of oxy forms of these proteins is proposed and substantiated. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 479–482, July–August, 1999.     

Quadrupole relaxation enhancement and polarisation transfer in DMSO solution of [Bi(NO3)3(H2O)3]*18-crown-6 in solid state

ABSTRACT

¹H spin-lattice relaxation studies have been performed for pure [Bi(NO₃)₃(H₂O)₃]*18-crown-6 in powder and its solution in dimethyl sulfoxide (DMSO). The experiments have been carried out in the frequency range of 10?kHz–30?MHz and the temperature range of 240–277?K; at 277?K the solution is already frozen. The ¹H relaxation of pure [Bi(NO₃)₃(H₂O)₃]*18-crown-6 has been interpreted in terms of three dynamical processes. Quadrupole Relaxation Enhancement effects have been observed in the frozen DMSO solution of [Bi(NO₃)₃(H₂O)₃]*18-crown-6. The specific mechanisms of the ¹H spin-lattice relaxation enhancement have been discussed distinguishing between effects caused by time independent (residual) and fluctuating ¹H-²⁰⁹Bi dipole-dipole interactions.     

Valence state alternation of copper species doped in HY zeolite as revealed by paramagnetic relaxation enhancement NMR spectroscopy

Paramagnetic relaxation enhancement (PRE) solid-state NMR (ssNMR) was used to monitor the valence state alternation of copper species doped in HY zeolite during catalytic reaction processes. The combination of PRE ssNMR and in-situ NMR spectroscopy facilitates the detection of copper species as well as the monitoring of evolution from reactants, intermediates to products in heterogeneously catalyzed processes, which is of great importance for elucidating the detailed catalytic reaction mechanism.     

Study of energy transfer in a solution of coumarin 460 and rhodamine 6G by time-resolved laser-induced fluorescence spectroscopy

A multi-photon fast analog technique has been used to study nonradiative energy transfer from coumarin 460 to rhodamine 6G molecules. At low acceptor concentrations (<10^-2 mol/1) the fluorescence decay from coumarin deviates markedly from monoexponential behavior. The complex decay of the donor fluorescence reflects the time-dependent population of donor-acceptor pairs. Various energy transfer kinetics were investigated. The donor decay was found to be consistent with Förster kinetics and the critical energy transfer radius was found to be (5.46±0.10) nm.     

Orientational relaxation of pheophorbide-a molecules in the ground and in the first excited state measured by transient dichroism spectroscopy

We report on transient dichroism spectroscopy carried out on pheophorbide-a in ethanol to measure the response time of the pump-beam induced anisotropy after selective excitation at high excitation levels. From the observed time behaviors of induced absorption, transient amplification, and of the bleaching signal, the orientational relaxation times of pheophorbide-a in the first excited singlet state and in the ground state were obtained separately to be 370 and 250 ps, respectively. It is found that pheophorbide-a behaves like a spherical rotor in the first excited state, while in the ground state randomization of molecules is dominated by the rotation around its quasi-symmetry axis. Because of rotation free measurement of ordinary transient absorption spectra fail in the case of ground state depletion, the observed orientational relaxation time of the ground state have to be taken into account to fit the bleaching kinetics obtained from transient absorption spectra very well to determine the intersystem crossing yield of pheophorbide-a to be 0.46.     

Fluorescence resonance energy transfer between acridine orange and rhodamine 6G and analytical application in micelles of dodecyl benzene sodium sulfonate

A new method for the determination of erythromycin by energy transfer fluorescence quenching of acridine orange (AO)—rhodamine 6G (R6G) in micelles solution studied and established. It was found that the effective energy transfer could occur between AO and R6G in the dodecyl benzene sodium sulfonate at and Britton-Robinson buffer (BR, pH=5.72). The fluorescence intensity of R6G had been increased sharply. Erythromycin diminished the fluorescence intensity of R6G. The detection limit was up to 0.316 mg l⁻¹. The range of determining concentration of erythromycin was 0.75-15 mg l⁻¹. The relative standards deviation were 0.66-1.38% for six parallel determinations of erythromycin. The recoveries of erythromycin were 96.95-101.41%. The measurement was applied to the determination of capsules of erythromycin with good results.     

Determination of T1-spin-lattice relaxation time in a two-level system by continuous wave multiquantum electron paramagnetic resonance spectroscopy in a presence of tetrachromatic microwave irradiation

Applicability of continuous wave multiquantum EPR methods to study relaxation times at X-band is examined. Multiquantum transitions excited in a two-level system by tetrachromatic irradiation are used for these studies. The Bloch equation model is applied to simulate lineshapes of the three quantum transitions as a function of frequency difference between exciting fields. The dependence of multiquantum transition signals on relaxation times and microwave amplitude is shown. On this basis a method of deducing relaxation times from these signals is formulated. The case of a homogeneously and inhomogeneously broadened resonance line is considered. Two experimental methods are used to verify the proposed hypothesis: the X-band continuous wave multiquantum EPR with four frequencies microwave field and saturation recovery EPR. The values of T₁ obtained from CW MQ EPR and SR EPR are compared.     

Kinetics and mechanism of electron transfer reaction of single and double chain surfactant cobalt(III) complex by Fe2+ ions in liposome (dipalmitoylphosphotidylcholine) vesicles: effects of phase transition

In this study, we report the kinetics of reduction reactions of single and double chain surfactant cobalt(III) complexes of octahedral geometry, cis-[Co(en)₂(4AMP)(DA)](ClO₄)₃ and cis-[Co(dmp)₂(C₁₂H₂₅NH₂)₂](ClO₄)₃ (en = ethylenediamine, dmp = 1,3-diaminopropane, 4AMP = 4-aminopropane, C₁₂H₂₅NH₂ = dodecylamine) by Fe²⁺ ion in dipalmitoylphosphotidylcholine (DPPC) vesicles at different temperatures under pseudo first-order conditions. The kinetics of these reactions is followed by spectrophotometry method. The reactions are found to be second order and the electron transfer is postulated as outer sphere. The remarkable findings in the present investigation are that, below the phase transition temperature of DPPC, the rate decreases with an increase in the concentration of DPPC, while above the phase transition temperature the rate increases with an increase in the concentration of DPPC. The main driving force for this phenomenon is considered to be the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes. Besides, comparing the values of rate constants of these outer-sphere electron transfer reactions in the absence and in the presence of DPPC, the rate constant values in the presence of DPPC are always found to be greater than in the absence of DPPC. This is ascribed to the double hydrophobic fatty acid chain in the DPPC that gives the molecule an overall tubular shape due to the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes more suitable for vesicle aggregation which facilitates lower activation energy, and consequently higher rate is observed in the presence of DPPC. The activation parameters (ΔS^# and ΔH^#) of the reactions at different temperatures have been calculated which corroborate the kinetics of the reaction.