A role of solvent in vibrational energy relaxation of metalloporphyrins

The formation of a vibrationally excited photoproduct of metalloporphyrins upon (π, π*) excitation and its subsequent vibrational energy relaxation were monitored by picosecond time-resolved resonance Raman spectroscopy. Stokes Raman bands due to a photoproduct of nickel octaethylporphyrin (NiOEP) instantaneously appeared upon the photoexcitation. Their intensities decayed with a time constant of 300 ps, which indicates electronic relaxation from the (d, d) excited state (B_1g) to the ground state (A_1g), being consistent with the results of transient absorption measurements by Holten and coworkers. Anti-Stokes ν₄ and ν₇ bands for vibrationally excited (d, d) state of NiOEP decayed with time constants of 10 and 300 ps. The former is ascribed to vibrational relaxation, while the latter corresponds to the electronic relaxation from the (d, d) excited state to the electronic ground state. While the rise of anti-Stokes ν₄ intensity was instrument-limited, the rise of anti-Stokes ν₇ intensity was delayed by 2.6±0.5 ps, which indicates that intramolecular vibrational energy redistribution has not been completed in subpicosecond time regime. To study a mechanism of intermolecular energy transfer, solvent dependence of the time constants of anti-Stokes kinetics was investigated using various solvents. No significant solvent dependence of the rise and decay constants was observed for NiOEP. For an iron porphyrin, we observed two phases in intermolecular energy transfer. The fast phase was insensitive to solvent and the slow phase depended on solvents. A model of classical thermal diffusion qualitatively reproduced this behavior. For solute-solvent energy transfer process, low-frequency modes of proteins seem to be less important.     

Ultrafast proton transfer dynamics of 2-(2'-hydroxyphenyl)benzoxazole dye in different solvents

The excited-state intramolecular proton transfer of 2-(2-hydroxyphenyl)benzoxazole dye in different solvents is investigated using ultrafast femtosecond transient absorption spectroscopy combined with quantum chemical calculations.Conformational conversion from the syn-enol configuration to the keto configuration is proposed as the mechanism of excited-state intramolecular proton transfer.The duration of excited-state intramolecular proton transfer is measured to range from 50 fs to 200 fs in different solvents.This time is strongly dependent on the calculated energy gap between the N-S;and T-S;structures in the S;state.Along the proton transfer reaction coordinate,the vibrational relaxation process on the S;state potential surface is observed.The duration of the vibrational relaxation process is determined to be from8.7 ps to 35 ps dependent on the excess vibrational energy.     

Investigation of intra- and intermolecular transfer processes by picosecond fluorescence gating

Fluorescence up-conversion is a promising technique for the investigation of ultrafast processes within and between poly-atomic molecules. Conditions are discussed for up converting broad-band fluorescence efficiently with a time resolution better than 1 ps. Experimental results are presented on vibrational relaxation in the first excited singlet state, internal conversion, and intermolecular energy transfer in liquid solutions.     

Rapidly progressing photophysical and photochemical relaxation processes in complex organic molecules

Using methods of high-speed kinetic laser spectroscopy, we investigated the dynamics and mechanisms of rapidly progressing relaxation processes in multiatomic molecules. We separated intra- and intermolecular channels of relaxation of the vibrational energy of excitation by the rate of transformation of nonstationary absorption spectra in a picosecond range of times. The role of highly excited electronic states in the process of electronic-vibrational relaxation in molecules of the class of phenazines was ascertained. Applying femtosecond light pulses in a real time scale, we recorded the dynamics of the decay of optically induced anisotropy in rarefied vapors of organic compounds. Several mechanisms of transfer of a hydrogen atom in the process of formation of free radicals in photoreduction of ketones were established. The dynamics of formation of inter- and intramolecular exciplexes in binary gas-phase systems was investigated. We determined the mechanisms of intramolecular dissociation of a C–O chemical bond in spiropyrans and xanthene dyes. Photodissociation of S–S bonds in molecules of disulfides was studied. The possibility of the existence of states with intramolecular charge transport with a twisted configuration for organic free radicals is shown. To whom correspondence should be addressed. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 5, pp. 635–661, September–October, 1998.     

Geminate recombination of long-lived electron-hole pairs in doped carbazole-containing amorphous molecular semiconductors

This paper reports an investigation into the features of geminate recombination of long-lived electron-hole pairs in films of poly(N-epoxypropylcarbazole) (PEPC) containing intramolecular charge transfer compounds as centers of photogeneration of charge carriers carried out by measuring the attenuation kinetics of isothermal recombination luminescence over a wide range of temperatures (4.2–300 K) for times t>1 s, along with the kinetics of photoinduced EPR signals. A study is made of how the presence of a potential barrier to the reverse transition of carriers to the recombination center and the initial triplet state of the charged pairs affects the geminate recombination. It is established that the kinetics of isothermal recombintation luminescence attenuation follow the law I(t)∝t ^−m for the times under study, where m takes values from 0.65 to 1.05. The first observations of a nonmonotonic change in m with temperature are reported (m passes through a minimum at a certain temperature), and a mechanism is proposed for recombination of charged pairs in PEPC containing intramolecular charge-transfer compounds as an explanation for this phenomenon. Fiz. Tverd. Tela (St. Petersburg) 39, 1183–1187 (July 1997)     

Direct observation of the vibrational energy redistribution in (CF<Subscript>3</Subscript>)<Subscript>2</Subscript>CCO molecules resonantly excited by femtosecond infrared laser radiation

The dynamics of multiphoton excitation of (CF₃)₂CCO molecules has been investigated under the condition of resonant action of femtosecond infrared laser radiation on the ν₁ vibrational mode of the C=C=O bond. It has been shown that the mode-selective excitation of this vibration occurs up to the ν = 6 level. The kinetics of the subsequent intramolecular vibrational energy redistribution from the ν₁ mode has been measured. A value of 5 ± 0.3 ps has been obtained for the characteristic time of this process.     

噁嗪750激光染料分子在醇类溶剂中超快动力学研究

利用飞秒时间分辨荧光亏蚀光谱技术,研究了噁嗪750激光染料分子在典型的醇类溶剂中超快动力学过程.实验发现两个超快动力学过程:飞秒量级的快速弛豫过程和皮秒量级的慢速弛豫过程.快速弛豫过程来源于分子内振动能量再分配(IVR)和溶剂分子超快惯性弛豫动力学过程,而慢速弛豫过程对应于溶剂化的扩散分子弛豫动力学过程.实验结果表明慢速弛豫过程的时间常数随醇溶剂分子间氢键键能的增强而增大.     

Investigation of non-equilibrium electron-hole plasma in nanowires by THz spectroscopy

Efficient emission of THz radiation by AlGaAs nanowires via excitation of photocurrent by femtosecond optical pulses in nanowires was observed. Dynamics of photoinduced charge carrier was studied via influence of electron-hole plasma on THz radiation by optical pump THz probe method. It was found that characteristic time of screening of contact field is about 15 ps. Recombination of non-equilibrium occurs in two stages: fast recombination of free electron and holes (with relaxation time about 700 ps), and slow recombination (with relaxation time about 15 ns), which involves a capture of electrons and holes on the defects of crystalline structure of nanowires.     

飞秒时间分辨拉曼光谱用于研究β-胡萝卜素单重激发态内转换和振动弛豫过程

搭建了飞秒时间分辨受激拉曼光谱(FSRS)装置,并用于研究全反式β-胡萝卜素单重电子激发态超快内转换和振动弛豫过程.基于三脉冲“抽运-探测”方案搭建的时间分辨受激拉曼光谱装置同时实现了150fs的时间分辨率和23.7cm^-1的光谱分辨率,光谱检测范围为300—4000cm^-1.对全反式β-胡萝卜素电子激发态的飞秒时间分辨拉曼光谱研究表明,β-胡萝卜素被激发到S₂态后,经由寿命约为0.3ps的中间态S_X态实 关键词： 飞秒时间分辨拉曼光谱 β-胡萝卜素 激发态内转换 振动弛豫     

液相硝基甲烷分子振动特性的相干反斯托克斯拉曼散射光谱

构建时间分辨相干反斯托克斯拉曼散射（CARS）光谱系统,从微观层次研究硝基甲烷的分子相干振动动力学特性.实验中采用超连续白光作为斯托克斯光,通过调整斯托克斯光的时间延迟,得到不同振动模式的CARS光谱.通过对振动弛豫曲线的拟合,获得硝基甲烷分子不同振动模式的振动失相时间.结果表明C–H键伸缩振动比C–N键伸缩振动更容易受热声子的影响.在热加载下,硝基甲烷分子的C–H键有望首先被激发并引起初始化学反应.     

Study of femtosecond dynamics in vibrationally excited free bis(trifluoromethyl)ketene and metal carbonyl molecules induced by CO bond resonant excitation

The dynamics of relaxation processes in free bis(trifluoromethyl)ketene (CF₃)₂CCO and Fe(CO)₅ and Cr(CO)₆ metal carbonyl molecules after multiphonon excitation of the C=C=O and C=O vibrations by femtosecond laser infrared radiation was studied. The temporal and spectral dependences of the relaxation of the excited vibrational states were measured. Kinetics with a characteristic decay time of about 5 ps was obtained for (CF₃)₂CCO molecules. Its behavior is interpreted as a manifestation of the intramolecular relaxation of the excited vibration states of the resonance mode. Kinetic curves with characteristic times of about 250–500 fs were observed for Fe(CO)₅ and Cr(CO)₆. The behavior of these curves depends on the mutual orientation of the polarizations of the pump and probe pulses.     

Kinetics of CO Molecules Taking into Account Resonant VE Exchanges in a Nonequilibrium Nozzle Flow

The kinetics of CO molecules with excited electronic levels for a nonequilibrium flow in nozzles is studied. Three electronic energy levels are taken into account; the VV exchanges of the vibrational energy within each electronic energy level, VT transitions from the vibrational energy to the translational energy, and VE exchanges between the vibrational energy and the electronic terms occur in the system. The system of equations of vibrational level kinetics and gasdynamics, which is written in the zeroth approximation of the Chapman–Enskog method, is solved numerically. Special attention is paid to estimating the effect of the VE exchanges of the vibrational energy on the formation of nonequilibrium populations of the vibrational levels. It is shown that resonant VE transitions considerably affect the relaxation process and noticeably change the population of the upper vibrational levels even in the absence of recombination and dissociation processes; VE exchanges also affect the time dependence of the vibrational temperature.     

载流子复合对时间分辨法拉第旋转光谱的影响

利用二能级体系速率方程,推导了半导体中探测光探测到的法拉第旋转光谱的理论模型,发现电子-空穴对的复合对法拉第旋转信号随时间的衰减有重要影响,并利用该模型对GaAs量子阱中实验测得的法拉第旋转光谱进行拟合,得到GaAs量子阱材料中的电子自旋弛豫时间为73.5 ps,而直接利用单指数进行拟合得到的电子自旋弛豫时间仅为51.3 ps. 因此,直接利用单指数对法拉第旋转光谱进行拟合得到电子自旋弛豫时间的传统做法是不准确的. 关键词： 自旋弛豫时间 时间分辨法拉第旋转光谱 GaAs量子阱     

Contribution a l'etude des mecanismes de relaxation dielectrique des amines primaires dans le domaine ultra-hertzien

The authors have studied the mechanism of dielectric relaxation of primary amines from the point of view of the following characteristics : relaxation time distribution, activation energy, resultant behaviour of autocorrelation function of the orientational polarisation, spectral density of energy as a function of temperature and chain length of the aliphatic type molecules.The analysis of the relaxation mechanism is made on the basis of semi-empirical macroscopic model of Davidson-Cole. The relaxation mechanism can be analysed as a function of the combined effects of intermolecular and intramolecular relations which are related to the dipolar behaviour of amine group as well as the effect of hydrocarbonic aliphatic chain.     

Double electron-electron resonance in electron spin echo: Conformations of spin-labeled poly-4-vinilpyridine in glassy solutions

Double electron-electron resonance in electron spin echo has been used to study the glassy solutions of poly-4-vinylpyridine doped by nitroxyl radicals frozen in liquid nitrogen. The phase relaxation of spin labels due to spin-spin interaction of unpaired electrons has been studied. The intramolecular and intermolecular contributions of the dipole-dipole interaction of spin labels into relaxation process have been separated. It has been established that both the intramolecular and intermolecular spin-spin interaction of spin labels lead to the dependence of echo signal on timeT of the exp (?aT ^q ) type. It is shown that for the intramolecular interaction the experimentalq value is 0.3, for the intermolecular one it is 2. The assumption has been made of the linear structure of polymeric molecules due to the presence of a sufficiently high density of an electric charge on polymeric molecules.     

Intermolecular and intramolecular contributions to the relaxation process in sorbitol and maltitol

Molecular mobility in sorbitol and maltitol is studied with spectroscopic techniques and molecular dynamics simulations in order to evaluate the relative contributions of the intermolecular and intramolecular interactions involved in the relaxation processes. The results of the molecular dynamics simulations performed on the polyols in the bulk or in vacuum compares well with the results of the analysis of the relaxation diagrams in the framework of the Perez et al. model. They both imply that the difference in the relative contributions of the intermolecular and intramolecular interactions associated with the different chemical architectures of the two polyols must be taken into account. The intermolecular interactions cannot be neglected and they are stronger in sorbitol than in maltitol in relation with the linear structure of this polyol. The intramolecular barrier, higher in the maltitol molecule with a more complex structure, could be at the origin of the higher junction temperature between the α and β relaxation processes.     

Photoluminescence kinetics of multiperiod GaAs/AlGaAs structures with asymmetric barriers promising for making unipolar lasers

Photoluminescence kinetics in multiperiod GaAs/AlGaAs quantum-well structures with asymmetric barrier heights has been investigated. Owing to the barrier asymmetry, a time constant of nonradiative recombination between the laser subbands of 9 ps has been achieved, which is record long for unipolar lasers and exceeds the nonradiative relaxation time constant of the lower laser subband. This provides population inversion in the system. Efficient suppression of an unwanted cascade transition between the laser subbands via quasi-continuum states has been demonstrated.     

Size-dependent optical properties and carriers dynamics in CdSe/ZnS quantum dots

Size-dependence of optical properties and energy relaxation in CdSe/ZnS quantum dots （QDs） were investigated by two-colour femtosecond （fs） pump-probe （400/800 nm） and picosecond time-resolved photoluminescence （ps TRPL） experiments. Pump-probe measurement results show that there are two components for the excited carriers relaxation, the fast one with a time constant of several ps arises from the Auger-type recombination, which shows almost particle sizeindependence. The slow relaxation component with a time constant of several decades of ns can be clearly determined with ps TRPL spectroscopy in which the slow relaxation process shows strong particle size-dependence. The decay time constants increase from 21 to 34 ns with the decrease of particle size from 3.2 to 2.1 nm. The room-temperature decay lifetime is due to the thermal mixing of bright and dark excitons, and the size-dependence of slow relaxation process can be explained very well in terms of simple three-level model.     

Molecular dynamics study of the vibrational relaxation of OCl and OCl in the bulk and the surface of water and acetonitrile

The vibrational relaxation of OCl and OCl⁻ in the bulk and the liquid/vapor interface of water and acetonitrile is studied by molecular dynamics computer simulations. Both equilibrium calculations of the vibrational friction and non-equilibrium simulation of the energy relaxation are used to elucidate the factors that influence the rate of energy relaxation in systems that represent polar ionic and non-ionic solutes in polar protic and non-protic solvents. We find that, in agreement with previous experimental and theoretical studies, the relaxation of the ionic solute is much faster than that of the non-ionic solute in both the solvents. However, while the relaxation is slowed down considerably when the non-ionic solute is transferred from the bulk to the interface, no such surface effect is found in the case of the ionic solute. This behavior can be explained by noting that the ionic solute is able to keep its first solvation shell intact upon transfer to the interface and that the main contribution to the friction is due to the Lennard-Jones part of the intermolecular potential.     

Vibrational-kinetics methods and their applications to molecular lasers and laser chemistry

The vibrational kinetics of molecules simulated by anharmonic oscillators is developed under essentially nonequilibrium conditions. Analytic expressions are obtained for the vibrational distribution function, the relaxation time, and the dependence of the vibrational energy on the pump power; the limiting capacity of the energy reservoir of the anharmonic molecules is estimated. Vibrational kinetics is investigated in mixtures and a redistribution of the vibrational energy among the modes is observed as a function of the component concentration. The singularities of vibrational relaxation in liquids and molecular crystals, due to collective interactions, are studied. A number of concrete applications are considered: the rate of nonequilibrium dissociation is calculated, an analytic model is developed for the CO laser, isotope separation in chemical reactions of vibrationally excited molecules is investigated, and a new type of lasers based on intramolecular transitions in liquids and molecular crystals is proposed.The article represents the contents of a dissertation submitted for the degree of Candidate of Physicomathematical Sciences. Guidance chairmen-Doctor of physicomathematical sciences A. L. Shelepin and Candidate of physicomathematical sciences B. F. Gordiets. Defended 27 October 1975 at the P. N. Lebedev Physics Institute of the Academy of Sciences of the USSR.Translated from Trudy Ordena Lenina Fizicheskogo Instituta im. P. N. Lebedeva, Akademii Nauk SSSR, Vol. 107, pp. 3–67, 1979.