Rydberg states in the condensed phase studied by fluorescence depletion spectroscopy

Higher Rydberg states of NO trapped in rare gas matrices have been studied by inducing Rydberg-Rydberg transitions from the lowest Rydberg state and detecting its fluorescence depletion. This technique unravels Rydberg states, which cannot be accessed by ground state absorption. However, no clear cut Rydberg series show up. The data show a compression of the n-(n + 1) splittings between Rydberg states, as well as of the splittings. The results are rationalised in terms of the quantum defect model and the lack of extended Rydberg series is due to the compression of high-n Rydberg states in a tiny energy region below the ionisation potential. Finally, fluorescence depletion data of NO trapped in amorphous sites (the so-called red sites) of solid Ar can be interpreted in terms of the gas phase NO-Ar van der Waals data. A general discussion on the fate of Rydberg states in van der Waals complexes, in liquids, and in solids is presented in an attempt to relate the data in these different media. Received 28 July 1999 and Received in final form 8 November 1999     

Rapid internal conversion in a symmetric molecule LD 700 studied by means of femtosecond fluorescence depletion

The rapid internal conversion dynamics at room temperature is determined by using the femtosecond time-resolved fluorescence depletion measurements of a complex solvated molecule of LD 700 (rhodamine 700) combined with steady-state absorption and fluorescence spectroscopy, as well as quantum chemical calculation. The molecule is excited by a 50fs laser pulse at 400nm which directly populated the highly excited singlet state, the rapid internal conversions (ICs) are observed, which leads to the directional changes of the emission transition moment following photoexcitation to the highly excited singlet state S₅ of LD 700.     

Investigation of free radicals induced by light ions in CR-39 using ESR spectroscopy

In previous investigations the formation of radicals induced by γ-irradiation in CR-39 samples has been studied by electron spin resonance (ESR) spectroscopy. On the other hand, all attempts fail to detect radicals in samples irradiated by particles (p, and neutrons). The present work succeeded in detection of radicals produced by charged particle radiation in CR-39 (TASTRAK). The detectors were irradiated with protons of 7 MeV and -particles of 3 MeV with fluences in the order of 10¹¹–10¹² particles/cm². The observed ESR signal is composed of at least four different resonance lines for each of which we determined the amplitudes, g-factors, lifetimes and the G-value. The amplitude of the total ESR signal decreases rapidly with a short and a longer lifetime. About 5 days after irradiation the ESR intensity decreased to an undetectable value. The lowest detectable dose (LDD) is of the order of 1 kGy.     

The adsorption of CO on Cu surfaces studied by electron energy loss spectroscopy

Electron energy loss spectroscopy (ELS) in the energy range of electronic transitions (primary energy 30 < E₀ < 50 eV, resolution ΔE ≈ 0.3 eV) has been used to study the adsorption of CO on polycrystalline surfaces and on the low index faces (100), (110), (111) of Cu at 80 K. Also LEED patterns were investigated and thermal desorption was analyzed by means of the temperature dependence of three losses near 9, 12 and 14 eV characteristic for adsorbed CO. The 12 and 14 eV losses occur on all Cu surfaces in the whole coverage range; they are interpreted in terms of intramolecular transitions of the CO. The 9 eV loss is sensitive to the crystallographic type of Cu surface and to the coverage with CO. The interpretation in terms of d(Cu) → 2π¹(CO) charge transfer transitions allows conclusions concerning the adsorption site geometry. The ELS results are consistent with information obtained from LEED. On the (100) surface CO adsorption enhances the intensity of a bulk electronic transition near 4 eV at E₀ < 50 eV. This effect is interpreted within the framework of dielectric theory for surface scattering on the basis of the Cu electron energy band scheme.     

Brownian diffusion of gold nanoparticles in an optical trap studied by fluorescence correlation spectroscopy

The effect of thermal-induced Brownian motion on gold nanoparticles (Au NPs) in optical traps is studied by fluorescence correlation spectroscopy (FCS) method. The Brownian motion and optical trapping potential are investigated by the decay time of the FCS curve and the laser power. It is shown that that the probability of finding a gold nanoparticle in the trap depends on the ratio of the optical energy of the particle to its thermal energy. A power threshold is observed by the decay time as a function of laser power. The experimental studies show that the temperature rise does not seriously affect the average number of particles in the focal spot, but the average residence time is more sensitively affected by the temperature.     

A transient layer in sendust on a silicon substrate,as studied by conversion electron Mössbauer spectroscopy

The conversion electron Mössbauer spectra of thin layers of Sendust on a silicon substrate were measured at room temperature. It is shown that a transient layer exists in which the composition deviates from the ideal Sendust composition but in which the structure is still ordered.     

The valence band of some light rare-earth metals studied by photoemission spectroscopy

The valence bands of La, Ce, Pr, and Nd have been studied by ultraviolet photoelectron spectroscopy (UPS) (He II, hv=40.8 eV) and compared to results from X-ray photoelectron spectroscopy (XPS)(Mg Kα_{1, 2}). The energy positions of the $\text{4?}$ levels are in good agreement with earlier XPS results and calculations based on estimates from optical and thermodynamic data. The widths of the sd bands and the $\text{4?}$ levels and the relative emission intensities are discussed.     

Adsorption of firefly luciferase at interfaces studied by total internal reflection fluorescence spectroscopy

The adsorption of luciferase onto silica surfaces was studied by total internal reflection fluorescence (TIRF) spectroscopy. Two model surfaces were used: hydrophilic and hydrophobic silica. Luciferase adsorbed differently on these two surfaces. Initial kinetics of luciferase adsorption onto the hydrophilic surface showed that luciferase adsorbs over an adsorption energy barrier of 3 kT The quantum yield of luciferase fluorescence decreased at the hydrophilic silica surface, which indicated that the protein conformation was altered during adsorption. Luciferase adsorption onto the hydrophobic silica surface proceeded with a small adsorption energy barrier and the fluorescence efficiency of adsorbed protein remained unchanged after adsorption. The affinity of luciferase for luciferin was measured using quenching of luciferase fluorescence with luciferin. The binding constant of the adsorbed luciferase-luciferin complex at the hydrophilic silica surface was two orders of magnitude smaller than the respective binding constant in the solution. Adsorbed luciferase showed an absence of ATP-dependent visible luminescence, indicating that the adsorbed enzyme was not active at either of the two silica surfaces.     

Inversionless amplification of light by a two-level medium as a result of mechanical-to-electromagnetic atomic energy conversion

Nonreciprocal effects in the acousto-optical interaction in gyrotropic cubic crystals with electroinduced anisotropy are studied. It is shown that the presence of optical gyrotropy leads to the doubling of the number of peaks of amplitude nonreciprocity, whereas an external electric field causes their shift and enhancement. It is found that the direction of lasing in a ring laser can be reversed by changing the direction of the control field. The results obtained can be used for the development and optimization of polarization-and electro-controlled acousto-optical nonreciprocal elements on the basis of cubic gyrotropic crystals.     

Effect of ion bombardment at low energy on (100)InP surfaces,studied by Auger electron spectroscopy

Surface cleaning of (100)InP substrates with an Ar⁺ ion beam of 250–400 eV is analysed by AES and shown as a function of time. The results obtained show the possibility of removing the contamination layer without any significant chemical damage to the InP surface.     

Electronic excitation processes in rare gas clusters studied by electron energy loss spectroscopy

We present the electron energy loss spectra for Ar clusters as a function of incident electron energy and of cluster size. In spectra measured with 100 eV incident electron energy the bulk excitation peak becomes visible for a mean cluster size above 170 atoms per cluster. For 250 eV incident electron energy the bulk excitation peak is clearly observable even for a mean cluster size of 120 atoms per cluster. These experimental results are qualitatively reproduced by a simple calculation that accounts for the mean free path of electrons in Ar clusters; i.e., the penetration depth of incident electrons into the cluster.     

Intensity correlation spectroscopy of the resonance fluorescence light of two-atomic molecules

The spectroscopic application of intensity correlation measurements of the resonance fluorescence light from two-atomic molecules is proposed. It is shown that from the intensity correlation function not only the natural line width of the electronic transition and the electron-vibration coupling strength but also very narrow homogeneous vibrational line widths can be determined without any use of a spectral apparatus.     

荧光光谱法研究核黄素与核黄素结合蛋白的相互作用

运用荧光光谱研究了核黄素与核黄素结合蛋白的相互作用,并探讨了两者间的结合类型、结合常数、结合过程中热力学参数和能量转移。结果表明:核黄素结合蛋白内源荧光的猝灭是由于核黄素与蛋白质之间形成复合物,并符合静态猝灭机理。298,308,318K下核黄素与核黄素结合蛋白的结合常数分别为:5.35×108,1.54×108,0.56×108 L.mol-1。热力学数据表明核黄素与核黄素结合蛋白之间主要作用力为氢键和范德华力。Frster能量转移理论确定了核黄素与核黄素结合蛋白的作用距离与能量转移效率分别为0.70nm与0.39。利用同步荧光光谱研究了核黄素结合蛋白与核黄素结合过程中构象的变化。     

Metal interface formation studied by high-energy reflection energy loss spectroscopy and electron Rutherford backscattering

We demonstrate that high-energy, high-resolution reflection electron energy loss spectroscopy can provide unique insights into interface formation, especially for the case where an extended interface is formed. By changing the geometry and/or electron energy the electronic structure can be probed over a range of thicknesses (from 10s of Å to more than 1000 Å). At the same time one resolves the elastically scattered electrons into different components, corresponding to scattering of atoms with different mass (so-called ‘electron Rutherford backscattering’). Thus these high-energy REELS/elastic scattering experiments obtain information on both the electronic structure and the atomic composition of the overlayer formed.     

High pressure stability of protein complexes studied by static and dynamic light scattering

The high pressure dissociation of hemocyanin prepared from the lobster Homarus americanus and casein micelles from cow milk were observed by in situ light scattering. The hemocyanin dodecamer dissociated via a hexamer into monomers in a two-step three-species reaction. The influence of ligands and the effector l-lactate on the dissociation behavior was investigated. While no effect by carbon monoxide after exchanging the ligand oxygen was observed, the addition of the effector l-lactate led to a decrease in the pressure stability. Due to a trimer intermediate which was found to be stabilized by l-lactate, the dissociation reaction in the presence of the effector was analyzed by a three-step four-species reaction. In the case of casein micelles, a two-step dissociation mechanism was found. The stabilizing interactions of casein micelles were identified and separated.     

Efficiency of energy transfer by resonance in quenching of protein fluorescence by dyes

Considering the quenching of tryptophan fluorescence of bovine serum albumin by various dyes as an example, it is shown that overlap of radiation and absorption spectra does not necessarily lead to energy transfer by resonance. No correlation is revealed between the limiting quenching and the Forster overlap integral. Quenching can occur even in the absence of overlap. The magnitude of energy transfer is markedly lower than that of quenching owing to competing processes, namely, excitation deactivation by the dye and, probably, by the protein itself which undergoes conformation upon sorption of the dye. Negatively charged and neutral dyes posses, on the average, a higher quenching activity relative to albumin than do positively charged dyes. Institute of the Biophysics of Cells of the Russian Academy of Sciences, Pushchino, 142292, Moscow Region, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 2, pp. 290–293, March–April, 1998.     

Selection rule effects in electronic excitations of chemisorbed molecules as studied by energy loss spectroscopy

Selection rule effects associated with long-range transition dipole scattering can be significant in electron energy loss spectroscopy (ELS) for loss energies up to ～10–12 eV (or higher) on a variety of metal and semiconductor surfaces. These effects will appear in ELS studies of the electronic excitations of chemisorbed molecules; in particular, selection rule effects will suppress the intensity of certain low-lying valence transitions in several cases of current interest in chemisorption.     

Depth-resolved fluorescence measurement in a layered turbid medium by polarized fluorescence spectroscopy

We show that, when a turbid medium with a layered fluorophore distribution is excited by linearly polarized light, measurement of angle-resolved polarized fluorescence can provide depth-resolved fluorescence measurements.