Nonequilibrium charge recombination from the excited adiabatic state of donor-acceptor complexes

A model of nonequilibrium charge recombination from an excited adiabatic state of a donor-acceptor complex induced by the nonadiabatic interaction operator is considered. The decay of the excited state population prepared by a short laser pulse is shown to be highly nonexponential. The influence of the excitation pulse carrier frequency on the ultrafast charge recombination dynamics of excited donor-acceptor complexes is explored. The charge recombination rate constant is found to decrease with increasing excitation frequency. The variation of the excitation pulse carrier frequency within the charge transfer absorption band of the complex can alter the effective charge recombination rate by up to a factor 2. The magnitude of this spectral effect decreases strongly with increasing electronic coupling.     

Excitation Frequency Dependence of Ultrafast Photoinduced Charge Transfer Dynamics

The dependence of the photoinduced charge transfer rate constant on the pump pulse carrier frequency is shown to be strong, and it is considerably affected by the value of the reorganization energy of low‐frequency modes at the stage of excitation. In the area of small values of the reorganization energy, the dependence of the charge transfer rate constant on the pump pulse carrier frequency is strongly nonmonotonic that is caused by vibrational resonances and variation of the initial position of the wave packet on the term of the locally excited state. Increasing the reorganization energy smoothes the dependence. The smoothing is caused by the broadening of the vibrational resonances and their overlapping. The high‐frequency vibrational mode excitation typically accelerates the charge transfer in both areas of high and low exergonicity and decelerates it in the vicinity of the Marcus barrierless region.     

Excited states of the high-frequency vibrational modes and kinetics of ultrafast photoinduced electron transfer

The effect of the carrier frequency of the exciting laser pulse on the kinetics of intramolecular photoinduced charge transfer in the multi-channel stochastic model is studied. It is shown that the population of different states of high-frequency intramolecular modes upon varying the frequency of the excitation pulse can considerably alter the rate constant of ultrafast charge transfer. It is found that a negative vibrational spectral effect is expected in the vicinity of a barrier-free area (the rate constant of photoinduced charge transfer decreases along with the carrier frequency of the excitation pulse), while a positive effect is predicted in areas of high and low exergonicity (an inverse dependence). It is concluded that the value of the spectral effect falls along with the time of vibrational relaxation. For ultrafast photo-induced charge transfer, however, it remains considerable up to relaxation times of 100 fs.     

微流控非接触电导检测芯片的设计与模拟

采用微加工技术制作了微芯片非接触电导检测系统。考察了激励电压、激励频率、样品溶液浓度对输出信号的影响,采用wewb 5.0软件对检测池的模拟电路进行了仿真模拟。通过比较试验和模拟结果,发现两者具有较好的一致性,说明模拟电路较好地反映了非接触电导检测池的电气特性。     

氢化物发生与ICP/AES联用后等离子体的性质研究

本文通过测量电子密度ｎｅ,电子温度Ｔｅ,激发温度Ｔｅｘｃ及谱线强度,将氢化物进样同水溶液常规气动雾化进样对比,研究了氢化物进入ＩＣＰ后,对等离子体性质的影响。结果表明,由于氢化物的引入,ＩＣＰ的激性能得到了改善。     

The influence of changes in the dipole moment of reagents on the rate of photoinduced electron transfer

The influence of spatial charge redistribution modeled by a change in the dipole moment of the reagent that experiences excitation on the dynamics of ultrafast photoinduced electron transfer was studied. A two-center model based on the geometry of real molecules was suggested. The model described photoexcitation and subsequent electron transfer in a donor-acceptor pair. The rate of electron transfer was shown to depend substantially on the dipole moment of the donor at the photoexcitation stage and the direction of subsequent electron transfer. These parameters also determined the most important characteristic of ultrafast photoinduced electron transfer, the angle ? between the reaction coordinates corresponding to these reaction stages. The regions of model parameters corresponding to the strongest influence of the carrier frequency of the exciting pulse on the rate of electron transfer were established.     

Effect of the excitation pulse frequency on the ultrafast photoinduced electron transfer dynamics

The dependence of the ultrafast photoinduced electron transfer dynamics in donor-acceptor complexes on the excitation pulse carrier frequency (spectral effect) has been investigated in the framework of a model involving three electronic state. The spectral effect has been shown to strongly depend on the angle theta between the reaction coordinate directions corresponding to optical and charge transfer transitions. Describing the solvent as a linear homogenous polar medium and accounting for Coulombic interaction of the transferred charge with the medium polarization fluctuations, the angle theta has been found out to be typically in the area 40 degrees -85 degrees. Exactly in this area of theta the spectral effect is predicted to be most pronounced.     

Femtosecond time-resolved two-photon photoemission studies of electron dynamics in metals

Electron-hole excitation and relaxation in the bulk, at interfaces, and surfaces of solid state materials play a key role in a variety of physical and chemical phenomena that are important for surface photochemistry, particle-surface interactions, and device physics. Information on charge carrier relaxation in metals can be obtained through analysis of linewidths measured by photoemission and related techniques, which give an estimate of the upper limit for electron and hole relaxation; however, many factors can contribute to spectral broadening, thus it is difficult to extract specific information on electronic relaxation processes. With femtosecond lasers it is possible to probe directly in a time-resolved fashion the charge carrier dynamics in metals by a variety of linear and nonlinear optical techniques. Femtosecond time-resolved two-photon photoemission has attracted particularly strong interest because it incorporates many of the surface analytical capabilities of photoemission and inverse photoemission — the traditional probes for surface and bulk band structures of solid state materials — with time-resolution that is approaching the fundamental response of electrons to optical excitation. Advances in the direct measurements of electron-hole excitation, charge carrier relaxation, and dynamics of intrinsic and adsorbate induced surface states are reviewed. With femtosecond lasers it also is possible to probe a variety of coherent phenomena, and even to control the charge carrier dynamics in metals through the optical phase of the excitation light. Pioneering experiments in this new field also are discussed.     

Investigations on evaporation phenomena in the plastic bonded electrodes used in emission spectroscopy by radioisotopic labelling

⁵¹Cr tracer was used to study the evaporation of chromium during excitation. The evaporation rate vs. time relationships and the isotope distribution in the carrier electrodes were investigated using different electrodes /graphite and carbon/ in the arc excitation of the non-conducting material mixed with the appropriate conducting material /graphite or carbon/. The mechanism of the transport was elucidated.     

Off-resonance excitation in a linear ion trap

Off-resonance excitation coupled with mass-selective axial ejection of ions in a linear ion trap is shown to allow coherent control of a trapped ion population. Oscillations of the detected ion current have been found to correspond to the degree of detuning of the excitation field from the resonance frequency. Under appropriate excitation conditions coherent oscillations at the excitation frequency are seen that evolve into the ions’ secular frequency on termination of the excitation field. Termination of the excitation field at various points during the off-resonance excitation profile leaves the ions with different degrees of radial excitation. The degree of radial excitation can be controlled by the coherent excitation field and is demonstrated to be useful for collision-induced dissociation.     

Site-selective luminescence spectroscopy of impurity centres in solids: Model calculations and experiment

A theoretical model is presented which describes quantitatively the elimination of the inhomogeneous broadening in luminescence spectra of inpurity centres on site-selective laser excitation. The model explains our experimental data showing a remarkable dependence of the excitation selectivity on the excitation frequency: there is a gradual disappearance of the selectivity upon increasing the excitation frequency within the 0-0 transition band of various impurity porphyrins in amorphous matrices.     

Charge recombination in excited donor-acceptor complexes with two absorption bands

The dynamics of charge recombination in a photoexcited donor-acceptor complex comprising 1,2,4-trimethoxybenzene (electron donor) and tetracyanoethylene (electron acceptor) in several polar solvents (acetonitrile, valeronitrile, and octanonitrile) was studied in terms of the stochastic approach. The Gibbs energy of charge recombination and the reorganization energies of the medium and quantum and vibrational degrees of freedom were found by fitting the stationary absorption spectrum. The electronic couplings were determined by analyzing the time dependences of the population of the ionic state in acetonitrile. A comparison of the numerical simulation results with the experimental data showed that the nonstationary model under consideration quantitatively described the dynamics of charge recombination and its dependence on the carrier frequency of excitation pulses and the relaxation properties of solvents. Original Russian Text ? V.N. Ionkin, A.I. Ivanov, E. Vauthey, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 4, pp. 791–797.     

Effect of power and carrier gas flow rate on the tolerance to water loading in inductively coupled plasma atomic emission spectrometry

The effects of the carrier gas flow rate and the power on the amount of water that can be tolerated by the plasma have been studied by ICP-AES. Pneumatic nebulization, ultrasonic nebulization associated with desolvation and laser ablation have been used to obtain wet, partially desolvated and dry aerosols. It has been found that water is beneficial in improving the plasma electron number density and the excitation temperature when so-called robust conditions are used, i.e. high power and low carrier gas flow rate. This can be explained by the release of hydrogen. Under these conditions, desolvation had almost no effect on the plasma characteristics. When non-robust conditions were used, the plasma was highly sensitive to water loading. Desolvation led to an improvement in the plasma conditions. In this instance, the addition of hydrogen was most useful to restore the properties of the plasma and to act as a load buffer to minimize the matrix effects. The plasma characteristics have been evaluated based on simple diagnostics such as the Mg II/Mg I line intensity ratio, the Fe excitation temperature, the Ar line and the Ar continuum.     

Two-dimensional fluorescence (excitation/emission) spectroscopy as a probe of complex chemical environments

We report a new application of fluorescence spectroscopy for the identification and characterization of chemical species in complex environments. Simultaneous collection of a dispersed fluorescence spectrum for every step of the laser wavelength results in a two-dimensional spectrum of emission versus excitation wavelengths. This two-dimensional fluorescence (2DF) spectrum yields quick and intuitive assignments of a multitude of peaks in the separate fluorescence excitation and dispersed fluorescence spectra as belonging to the same species. We demonstrate the technique with the measurement of 2DF spectra of a discharge of dilute benzene into a supersonic free jet. A multitude of rovibronic bands due to the C(2) Swan and C(3) comet bands are immediately apparent and even unreported bands can be assigned intuituvely. Custom software filters are employed to enhance or reject emission from one or the other carrier to obtain excitation spectra arising from purely one carrier, or even a specific spectral component of a single carrier. The very characteristic 2DF fingerprints of C(2) and C(3) permit identification of another unidentified species in the discharge that absorbs at 476 nm, coincident with one of the diffuse interstellar bands.     

Spatial distributions of metastable argon,temperature and electron number density in an inductively coupled argon plasma

Spatially resolved radial distributions of excitation temperature and electron number density in an argon ICP were obtained. The argon excitation temperature and electron number density near the plasma center were found to 7000 K and 5 × 10¹⁵ cm^?3, respectively, at an RF power of 1.5 kW and a carrier argon flow rate 0.65 1 min^?1.Various distributions of the absorbance at the Ar I 811.5 nm line, which has one of the metastable levels as the lower level, were obtained with and without carrier argon flow, where an MIP was used as a light source. Introduction of a large amount of potassium did not influence the distribution of the absorbance. The emission intensities at Ar I 811.5 nm were also measured for comparison.     

Structural luminescence spectra of biogenous porphyrins under selective laser excitation and dependence of this effect on excitation wavelength

Selective laser excitation removes an inhomogeneous width in wideband luminescence spectra of solid solutions of biogenous porphyrins resulting in spectra consisting of narrow zero-phonon lines and phonon sidebands. The effect depends strongly on excitation frequency and disappears gradually upon increasing this frequency within the inhomogeneously broadened pure electronic transition band.