A series of all-trans-carotenoids with N=9, 13, and 15 conjugated bonds has been studied by pump-probe and pump-deplete-probe spectroscopies to obtain a systematic analysis of the energy flow between the different electronic states. The ultrafast dynamics in the carotenoids are initialized by excitation to the S2 state and subsequently manipulated by an additional depletion pulse in the near-IR spectral range. The changes in the dynamics after depletion of the excited state population allowed differentiation of the excited state absorption into two components, a major one corresponding to the well known S1 state and the small contribution on the red wing of the S0-S2 absorption band originating from the hot ground state. We found no evidence for an additional electronically excited state, usually called S*. Instead, a deactivation mechanism that includes the hot ground state supports the observed results nicely in the framework of a simple three state model (S2, S1, and S0).
Stable Pd(0) and Rh(0) nanoparticles with small and narrow size distribution can be prepared from relative large and agglomerated transition-metal particles dispersed in 1-n-butyl-3methylimidazolium hexafluorophosphate ionic liquid by simple laser irradiation. The laser irradiation is a complementary method for the generation of stable metal colloids in ionic liquids and also for the regeneration of small-size nanoparticles that may result from their agglomeration after different applications.
Stable gold nanoparticles (AuNPs) were prepared by simple laser ablation of an Au foil placed inside or outside four ionic liquids (ILs), without the addition of any external chemical reagent. Irregular spherical AuNPs with a diameter range of 5 to 20 nm were produced after laser ablation of an Au foil located inside or outside the ILs 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI·BF4), 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI·PF6) and 1-(3-cyanopropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ((BCN)MI·NTf2). Additionally, whereas laser ablation inside the IL 1-n-butyl-3-methylimidazolium dicyanamide BMI·N(CN)2 produced flower-like shaped nanoparticles of about 50 nm in size, ablation outside this IL presented similar results to the others ILs studied, as determined by TEM and UV-Vis. The size and shape of the prepared NPs were related to where NP nucleation and growth occurred, i.e., at the IL surface or within the IL. Indeed, the chemical composition of the IL/air interface and surface ion orientation played important roles in the stabilization of the AuNPs formed by laser ablation outside the ILs.
Carbon nanodots (C-dots) with an average size of 1.5 and 3.0 nm were produced by laser ablation in different imidazolium ionic liquids (ILs), namely, 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI.BF4 ), 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI.NTf2 ) and 1-n-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (OMI.NTf2 ). The mean size of the nanoparticles is influenced by the imidazolium alkyl side chain but not by the nature of the anion. However, by varying the anion (BF4 vs. NTf2 ) it was possible to detect a significant modification of the fluorescence properties. The C-dots are much probably stabilised by an electrostatic layer of the IL and this interaction has played an important role with regard to the formation, stabilisation and photoluminescence properties of the nanodots. A tuneable broadband fluorescence emission from the colloidal suspension was observed under ultraviolet/visible excitation with fluorescence lifetimes fitted by a multi-exponential decay with average values around 7 ns.
The relaxation dynamics of carbon disulfide are investigated in mixtures with polystyrene (PS) using the time-resolved optical heterodyne-detected optical Kerr effect (OHD-OKE). The data are analyzed using both the model-dependent approach, which assumes four distinct temporal responses, and the model-independent Fourier transform approach, which generates a spectral response that can be compared with results obtained by depolarized Rayleigh scattering. A slow dynamics is observed for the OHD-OKE transient decaying exponentially with a time constant that varies from 1.68 ps for neat CS2 to 3.76 ps for the most concentrated CS2PS mixture. The increase of this time constant accompanies an increase in the viscosity of the mixture, so we can associate this component with the diffusive reorientation process of the induced polarizability anisotropy of the carbon disulfide in the mixture. The short-time nuclear response is characterized in the frequency domain by a broad band that peaks around 30 cm(-1) for neat carbon disulfide, and is associated with a complex relaxation pattern. The vibrational distribution shifts to higher frequencies when the PS concentration is increased in the mixture. This result is discussed in terms of an increase in the interaction strength between the PS phenyl rings and the carbon disulfide molecules.
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