Hyper-Rayleigh scattering with picosecond pulse trains

We propose a method for measuring hyper-Rayleigh scattering employing pulse trains produced by a Q-switched and mode-locked Nd:YAG laser. The use of the entire pulse train under the Q-switch envelope avoids the need of any device to scan the irradiance, as is usually done with nanosecond and femtosecond single-pulse lasers. To verify the feasibility of the technique, we performed measurements in different solutions of para-nitroaniline and compared the results with those obtained with nanosecond pulses. In both cases, the agreement with the hyperpolarizability values reported in the literature is about the same, but the measurements carried out with pulse trains are at least 20 times faster. Besides the advantage of acquisition speed, the use of pulse trains also allows the instantaneous inspection of slow luminescence contributions arising from multiphoton absorption. (C) 2008 Optical Society of America.

Effect of pH on non-photochemical quenching in spinach photsystem 2 particles as measured by picosecond fluorescence decay kinetics

Single photon timing was used to study picosecond chlorophyll a fluorescence decay kinetics of pH induced non-photochemical quenching in spinach photosystem 2 particles. The characteristics of this quenching are a decrease in chlorophyll a fluorescence yield as well as a decrease in photochemistry at low pH. Picosecond kinetics of room temperature fluorescence temporally resolve the individual components of the steady state fluorescence yield into components that are related to primary energy conversion processes in photosystem 2. Four components were resolved for dark adapted (Fo), light saturated (Fm), and chemically reduced (Nadithionite) photosystem 2 reaction centres. The fastest and slowest components, indicative of energy transfer to and energy capture by the photosystem 2 reaction centre and uncoupled ("dead") chlorophyll, respectively, were not affected by changing pH from 6.5 to 4.0. The two intermediate components, indicative of electron transfer processes within the reaction centre of photosystem 2, were affected by the pH change. Results indicate that the decrease in the steady state fluorescence yield at low pH was primarily due to the decrease in lifetime and amplitude of the slower of the intermediate components. These results imply that the decrease in steady state fluorescence yield at low pH is not due to changes in energy transfer to and energy capture by the photosystem 2 reaction centre, but is related to changes in charge stabilization and charge recombination in the photosystem 2 reaction centre.

Ultrafast charge separation in a photoreactive rhenium-appended porphyrin assembly monitored by picosecond transient infrared spectroscopy

Rhenium(bipyridine)(tricarbonyl)(picoline) units have been linked covalently to tetraphenylmetalloporphyrins of magnesium and zinc via an amide bond between the bipyridine and one phenyl substituent of the porphyrin. The resulting complexes, abbreviated as [Re(CO)(3)(Pic)Bpy-MgTPP][OTf] and [Re(CO)(3)(Pic)Bpy-ZnTPP][OTf], exhibit no signs of electronic interaction between the Re(CO)(3)(bpy) units and the metalloporphyrin units in their ground states. However, emission spectroscopy reveals solvent-dependent quenching of porphyrin emission on irradiation into the long-wavelength absorption bands localized on the porphyrin. The characteristics of the excited states have been probed by picosecond time-resolved absorption (TRVIS) spectroscopy and time-resolved infrared (TRIR) spectroscopy in nitrile solvents. The presence of the charge-separated state involving electron transfer from MgTPP or ZnTPP to Re(bpy) is signaled in the TRIR spectra by a low-frequency shift in the nu(CO) bands of the Re(CO)(3) moiety similar to that observed by spectroelectrochemical reduction. Long-wavelength excitation of [Re(CO)(3)(Pic)Bpy-MTPP][OTf] results in characteristic TRVIS spectra of the S-1 state of the porphyrin that decay with a time constant of 17 ps (M = Mg) or 24 ps (M = Zn). The IR bands of the CS state appear on a time scale of less than 1 ps (Mg) or ca. 5 ps (Zn) and decay giving way to a vibrationally excited (i.e., hot) ground state via back electron transfer. The IR bands of the precursors recover with a time constant of 35 ps (Mg) or 55 ps (Zn). The short lifetimes of the charge-transfer states carry implications for the mechanism of reaction in the presence of triethylamine.

Low-lying excited states and primary photoproducts of [Os-3(CO)(10)-(s-cis-L)] (L = cyclohexa-1,3-diene, buta-1,3-diene)] clusters studied by picosecond time-resolved UV/Vis and IR spectroscopy and by density functional theory

Combined picosecond transient absorption and time-resolved infrared studies were performed, aimed at characterising low-lying excited states of the cluster [Os-3(CO)(10)(s-cis-L)] (L= cyclohexa-1,3-diene, 1) and monitoring the formation of its photoproducts. Theoretical (DFT and TD-DFT) calculations on the closely related cluster with L=buta-1,3-diene (2') have revealed that the low-lying electronic transitions of these [Os-3(CO)(10)(s-cis-1,3-diene)] clusters have a predominant sigma(core)pi*(CO) character. From the lowest sigmapi* excited state, cluster 1 undergoes fast Os-Os(1,3-diene) bond cleavage (tau=3.3 ps) resulting in the formation of a coordinatively unsaturated primary photoproduct (1a) with a single CO bridge. A new insight into the structure of the transient has been obtained by DFT calculations. The cleaved Os-Os(1,3-diene) bond is bridged by the donor 1,3-diene ligand, compensating for the electron deficiency at the neighbouring Os centre. Because of the unequal distribution of the electron density in transient la, a second CO bridge is formed in 20 ps in the photoproduct [Os-3(CO)(8)(mu-CO)(2)- (cyclohexa-1,3-diene)] (1b). The latter compound, absorbing strongly around 630 nm, mainly regenerates the parent cluster with a lifetime of about 100 ns in hexane. Its structure, as suggested by the DFT calculations, again contains the 1,3-diene ligand coordinated in a bridging fashion. Photoproduct 1b can therefore be assigned as a high-energy coordination isomer of the parent cluster with all Os-Os bonds bridged.

Dinitrogen release from arylpentazole: A picosecond time-resolved infrared, spectroelectrochemical, and DFT computational study

p-(Dimethylamino)phenyl pentazole, DMAP-N5 (DMAP = Me2N−C6H4), was characterized by picosecond transient infrared spectroscopy and infrared spectroelectrochemistry. Femtosecond laser excitation at 310 or 330 nm produces the DMAP-N5 (S1) excited state, part of which returns to the ground state (τ = 82 ± 4 ps), while DMAP-N and DMAP-N3 (S0) are generated as double and single N2-loss photoproducts with η ≈ 0.14. The lifetime of DMAP-N5 (S1) is temperature and solvent dependent. [DMAP-N3]+ is produced from DMAP-N5 in a quasireversible, one-electron oxidation process (E1/2 = +0.67 V). Control experiments with DMAP-N3 support the findings. DFT B3LYP/6-311G** calculations were used to identify DMAP-N5 (S1), DMAP-N3 +, and DMAP-N in the infrared spectra. Both DMAP-N5 (S1) and [DMAP-N5]+ have a weakened N5 ring structure.

Study of picosecond processes of an intercalated dipyridophenazine Cr(iii) complex bound to defined sequence DNAs using transient absorption and time-resolved infrared methods

Picosecond transient absorption (TA) and time-resolved infrared (TRIR) measurements of rac-[Cr(phen)2(dppz)]3+ (1) intercalated into double-stranded guanine-containing DNA reveal that the excited state is very rapidly quenched. As no evidence was found for the transient electron transfer products, it is proposed that the back electron transfer reaction must be even faster (<3 ps).

Picosecond Dynamics of the Prototropic Reactions of 7-Hydroxyflavylium Photoacids Anchored at an Anionic Micellar Surface

Three water-insoluble, micelle-anchored flavylium salts, 7-hydroxy-3-octyl-flavylium chloride, 4`-hexyl-7-hydroxyflavylium chloride, and 6-hexyl-7-hydroxy-4-methyl-flavylium chloride, have been employed to probe excited-state prototropic reactions in micellar sodium dodecyl sulfate (SDS). In SDS micelles, the fluorescence decays of these three flavylium salts are tetraexponential functions in the pH range from 1.0 to 4.6 at temperatures from 293 to 318 K. The four components of the decays are assigned to Four kinetically coupled excited species in the micelle: specifically, promptly deprotonable (AH(+)*) and nonpromptly deprotonable (AH(h)(+)*) orientations of the acid in the micelle. the base-proton geminate pair (A*center dot center dot center dot H(+)), and the free conjugate base (A*). The initial prompt deprotonation to form the germinate pair occurs at essentially the same rate (k(d) similar to 6-7 x 10(10) s(-1)) for all three photoacids. Recombination of the germinate pair is similar to 3-fold faster than the rate of proton escape from the pair (k(rec) similar to 3 x 10(10) s(-1) and k(diss) similar to 1 x 10(10) s(-1)), corresponding to an intrinsic recombination efficiency of the pair of similar to 75%. Finally, the reprotonation of the short-lived free A* (200-350 ps, depending oil the photoacid) has two components, only one of which depends oil the proton concentration in the intermicellar aqueous phase. Ultrafast transfer of the proton to water and substantial compartmentalization of the photogenerated proton at the micelle surface Oil the picosecond time scale strongly suggest preferential transfer of the proton to preformed hydrogen-bonded water bridges between the photoacid and the anionic headgroups. This localizes the proton in the vicinity of the excited base much more efficiently than ill bulk water, resulting ill the predominance of geminate re reprotonation at the micelle surface.

Picosecond Dynamics of Proton Transfer of a 7-Hydroxyflavylium Salt in Aqueous-Organic Solvent Mixtures

The intermediacy of the geminate base proton pair (A*center dot center dot center dot H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base proton pair A*center dot center dot center dot H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*center dot center dot center dot H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec) of A*center dot center dot center dot H(+)) from the diffusion controlled rates (dissociation, k(diss) and formation, k(diff)[H(+)], of A*center dot center dot center dot H+), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)).

Picosecond nonlinearity of GeO2-Bi2O3-PbO-TiO2 glasses at 532 and 1,064 nm

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Gas-phase Lifetimes of Nucleobase Analogues by Picosecond Pumpionization and Streak Techniques

The picosecond (ps) timescale is relevant for the investigation of many molecular dynamical processes such as fluorescence, nonradiative relaxation, intramolecular vibrational relaxation, molecular rotation and intermolecular energy transfer, to name a few. While investigations of ultrafast (femtosecond) processes of biological molecules, e.g. nucleobases and their analogues in the gas phase are available, there are few investigations on the ps time scale. We have constructed a ps pump-ionization setup and a ps streak camera fluorescence apparatus for the determination of lifetimes of supersonic jet-cooled and isolated molecules and clusters. The ps pump-ionization setup was used to determine the lifetimes of the nucleobase analogue 2-aminopurine (2AP) and of two 2AP˙(H2O)n water cluster isomers with n=1 and 2. Their lifetimes lie between 150 ps and 3 ns and are strongly cluster-size dependent. The ps streak camera setup was used to determine accurate fluorescence lifetimes of the uracil analogue 2-pyridone (2PY), its self-dimer (2PY)2, two isomers of its trimer (2PY)3 and its tetramer (2PY)4, which lie in the 7–12 ns range.

Bathorhodopsin structure in the room-temperature rhodopsin photosequence: picosecond time-resolved coherent anti-Stokes Raman scattering.

Structural changes in the retinal chromophore during the formation of the bathorhodopsin intermediate (bathoRT) in the room-temperature rhodopsin (RhRT) photosequence (i.e., vision) are examined using picosecond time-resolved coherent anti-Stokes Raman scattering. Specifically, the retinal structure assignable to bathoRT following 8-ps excitation of RhRT is measured via vibrational Raman spectroscopy at a 200-ps time delay where the only intermediate present is bathoRT. Significant differences are observed between the C=C stretching frequencies of the retinal chromophore at low temperature where bathorhodopsin is stabilized and at room temperature where bathorhodopsin is a transient species in the RhRT photosequence. These vibrational data are discussed in terms of the formation of bathoRT, an important step in the energy storage/transduction mechanism of RhRT.

High-power picosecond pulse generation from a gain-switched violet diode laser

Generation of picosecond pulses with a peak power in excess of 7W and a duration of 24ps from a gain-switched InGaN diode laser is demonstrated for the first time.

Picosecond soliton propagation using nonlinear optical loop mirrors as intensity filters

The authors show that by inserting nonlinear optical loop mirrors into an optical fibre transmission line, 1.5 ps solitons may be transmitted over at least 750 km, with amplifiers spaced at 15 km intervals.