Femtosecond spectroscopy of optical excitations in single-walled carbon nanotubes: evidence for exciton-exciton annihilation

Frequency-resolved femtosecond transient absorption spectra and kinetics measured by optical excitation of the second and first electronic transitions of the (8,3) single-walled carbon nanotube species reveal a unique mutual response between these transitions. Based on the analysis of the spectra, kinetics, and their distinct amplitude dependence on the pump intensity observed at these transitions, we conclude that these observations originate from both the excitonic origin of the spectrum and nonlinear exciton annihilation.     

Electrochemical modification of Bi2S3 coatings in a nickel plating electrolyte

The electrochemical behavior of Bi₂S₃ coatings in Watts nickel plating electrolyte was investigated using the cyclic voltammetry, electrochemical quartz crystal microbalance, X-ray diffraction, and energy dispersive X-ray analysis methods. During the bismuth sulfide coating reduction in Watts background electrolyte in the potential region from −0.4 to −0.6 V, the Bi₂S₃ and Bi(III) oxygen compounds are reduced to metallic Bi, and the decrease in coating mass is related to the transfer of S²⁻ ions from the electrode surface. When the bismuth sulfide coating is reduced in Watts nickel plating electrolyte, the observed increase in coating mass in the potential region −0.1 to −0.4 V is conditioned by Ni²⁺ ions reduction before the bulk deposition of Ni, initiated by Bi₂S₃. In this potential region, the reduction of Bi(III) oxygen compounds can occur. After the treatment of as-deposited bismuth sulfide coating in nickel plating electrolyte at E = −0.3 V, the sheet resistance of the layer decreases from 10¹³ to 500–700 Ω cm. A metal-rich mixed sulfide Ni₃Bi₂S₂–parkerite is obtained when as-deposited bismuth sulfide coating is treated in Watts nickel plating electrolyte at a potential close to the equilibrium potential of the Ni/Ni²⁺ system and then annealed at temperatures higher than 120 °C.     

Excited-state dynamics of carotenoids in light-harvesting complexes. 2. Dissecting pulse structures from optimal control experiments

Dispersed multipump-probe (PPP) spectroscopy was used to explore the role of saturation, annihilation, and structured pulses in recent coherent control experiments on the light-harvesting 2 complex from Rhodopseudomonas acidophila (Herek et al. Nature 2002, 417, 533). We discuss the complimentary aspects between the PPP technique and coherent control studies, in particular the ability to dissect complicated pulse structures and the utility in exploring incoherent mechanisms. With the aid of a simple multistate model involving only population dynamics, we illustrate how the optimized structured pulses may be explained in terms of an interplay between excited-state populations, saturation, and annihilation. Furthermore, we discuss the experimental conditions that are required for incoherent effects to contribute to control experimental signals, with particular emphasis on pulse intensities, and show that the optimization of a ratio of conservative signals (i.e., not modulated by external dynamics) is required to exclude saturation effects from coherent control studies.     

Temperature effects on femtosecond transient absorption kinetics of semiconducting single-walled carbon nanotubes

We report femtosecond transient absorption kinetics measured for selected semiconducting single-walled carbon nanotubes at different temperatures between 77 and 290 K. The nanotubes are embedded in a thin polymethylmethacrylate film, and the dominance of individual species enabled to probe selectively the kinetics associated with two desired tube types, the (6,5) and (7,5) tubes. A strikingly similar temperature dependence is found between the maximum change in the amplitude of transient absorption kinetics, the overall decay time and steady-state fluorescence emission intensity. The simplest explanation for our data is that the temperature dependence of the fluorescence intensity and the exciton decay kinetics are dominated by nonradiative decay and that the radiative decay rate is weakly temperature dependent.     

Asymptotic Expansions of Large Deviations for Sums of Nonidentically Distributed Random Variables

The work is designated for obtaining asymptotic expansions and determination of structures of the remainder terms that take into consideration large deviations both in Cramer zones and Linnik power zones for the distribution function of sums of independent nonidentically distributed random variables (r.v.). In this scheme of summation of r.v., the results are obtained first by mainly using the general lemma on large deviations considering asymptotic expansions for an arbitrary r.v. with regular behaviour of its cumulants [11]. Asymptotic expansions in the Cramer zone for the distribution function of sums of identically distributed r.v. were investigated in the works [1,2]. Note that asymptotic expansions for large deviations were first obtained in the probability theory by J. Kubilius [3].     

Mode-locking of neodymium lasers by glasses doped with PbS nanocrystals

Nonlinear optical absorption properties of silicate glasses doped by the PbS nanocrystals were investigated by means of the picosecond pump-probe absorption spectroscopy and absorption bleaching technique. The glass samples were used as saturable absorbers for passive mode-locking of Nd:YAG and Nd:glass lasers. Application of the PbS doped glass together with the active mode-locking and laser cavity quality control enabled the stable of generation of 28 ps and 5 ps duration pulses in Nd:YAG and Nd:glass lasers respectively. PACS 42.60.Fc; 42.70.Hj; 78.47.+p     

Theorems on Large Deviations for Randomly Indexed Sum of Weighted Random Variables

In this paper, we consider a random variable \(Z_{t}=\sum_{i=1}^{N_{t}}a_{i}X_{i}\), where \(X, X_{1}, X_{2}, \ldots\) are independent identically distributed random variables with mean E X=μ and variance D X=σ ²>0. It is assumed that Z ₀=0, 0≤a _i <∞, and N _t , t≥0 is a non-negative integer-valued random variable independent of X _i , i=1,2,…?. The paper is devoted to the analysis of accuracy of the standard normal approximation to the sum \(\tilde{Z}_{t}=(\mathbf{D}Z_{t})^{-1/2}(Z_{t}-\mathbf{E}Z_{t})\), large deviation theorems in the Cramer and power Linnik zones, and exponential inequalities for \(\mathbf{P}(\tilde{Z}_{t}\geq x)\).     

Nonlinear Exciton Annihilation and Local Heating Effects in Photosynthetic Antenna Systems

Abstract— Generation of the nonequilibrium distribution of excited vibrational modes stimulated by electronic energy relaxation in pigment-protein complexes of the light-harvesting antenna of some photosynthetic systems is discussed in this paper. It is shown that the simplest approach to this problem can be achieved by introducing a local temperature, which is a good parameter for describing the nonequilibrium distribution of the local vibrational modes of the pigment molecules and its nearest protein surroundings. Then the transient absorption kinetics is determined by the kinetics of the excitation relaxation as I well as the heating/cooling of the local vibrational modes. Experimentally, this process can be investigated in the i singlet-singlet annihilation conditions that create the i greatest amount of local heating. The systems under in-: vestigation are trimers of bacteriochlorophyll a contain- i ing pigment-protein complexes from the green sulfur i bacterium Chlorobium tepid urn (so-called FMO complexes) and aggregates of the light-harvesting complexes of photosystem II (LHC2) from higher plants containing chlorophyll alb. It was shown that at 77 K the heat redistribution kinetics in LHC2 is on the order of 3040 ps and in FMO it is approximately equal to 26 ps. The local heating effect at room temperature is less pronounced; however, by using longer pulses and at higher excitation energies (on the order of a magnitude higher), an additional kinetics of hundreds of ps, also related to the heating/cooling process, was observed.     

Study of energy transfer during the collision of a molecular stream with a surface

A method of direct study of the energy transfer between a molecular stream and the surface of a solid body is described. The energy loss of particles (Ar, CO₂) colliding with metal surfaces (Cu, Fe, Ta) was measured at various temperatures. The capture of the molecules by these surfaces was observed, and the corresponding adsorption times were measured.The author wishes to thank N. V. Kamyshov for his part in this research.     

Relaxation pathways of excited N-(triphenylmethyl)salicylidenimine in solutions

Excited state relaxation of N-(triphenylmethyl)-salicylidenimine (MS1) in protic and aprotic solvents has been investigated by means of absorption pump-probe spectroscopy with femtosecond time resolution and fluorescence spectroscopy with picosecond time resolution. Short-lived excited states and long-lived photoproducts have been identified from the differential absorption spectra. Excited states and photoproducts were different under excitation of enol-closed and cis-keto tautomers. As a result, the commonly accepted excited state relaxation model of aromatic anils, which assumes an ultrafast transformation of excited enol-closed tautomers into cis-keto tautomers, has been modified. Performed quantum chemical calculations suggest that hydrogen-bonded ethanol molecules facilitate formation of cis-keto tautomers and are responsible for their different relaxation pathways in comparison with relaxation of excited enol-closed tauromers. Fluorescence decay on a nanosecond time scale was attributed to aggregated MS1 molecules.