Electron photodetachment from iodide in ionic liquids through charge-transfer-to-solvent band excitation

Solvation of iodide and electrons in an ionic liquid (N,N,N-trimethyl-n-propylammonium bis(trifluoromethanesulfonyl)imide; TMPA-TFSI) was studied through the absorption spectra of the charge-transfer-to-solvent (CTTS) state of iodide and of solvated electrons. The interaction between the TMPA cation and iodide was strong, whereas electrons were weakly solvated in TMPA-TFSI. We followed electron photodetachment from iodide to the ionic liquid and formation of the solvated electrons by observing absorption in the visible and near-infrared regions using a nanosecond laser flash photolysis method. The quantum yield of the photodetachment in TMPA-TFSI was estimated to be 0.34, which is much higher than that in a high-concentration aqueous salt solution previously reported. We also examined a reaction of the solvated electrons with the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (Bmim-TFSI) as a solute in TMPA-TFSI. The reaction rate was determined to be 5.3 x 10(8) M(-1) s(-1). The electrons before full solvation (dry electrons) reacted with Bmim cations efficiently. These observations suggest that the electrons in TMPA-TFSI can move easily before solvation.     

Effect of temperature on the absorption spectra of the solvated electron in 1-propanol and 2-propanol: Pulse radiolysis and laser photolysis studies at temperatures up to supercritical condition

The absorption spectra of solvated electrons in 1-propanol and 2-propanol have been investigated from 22 to 270 °C at a fixed pressure of 7 MPa, by using both nanosecond pulse radiolysis and laser photolysis techniques. The results show that, even up to supercritical conditions, it is still possible to measure unambiguously the absorption spectra of solvated electron in these two propanols. The peak positions of the absorption spectra show a red-shift (shifts to longer wavelengths) as temperature increases, similar to water and other alcohols, but the temperature efficiency, dE_max/dT, of 1-propanol is larger than that of 2-propanol. In addition, in clear contrast to that of pulse radiolysis, in laser photolysis experiments, an increase in the maximum absorbance of the absorption spectra of solvated electron with temperature up to ∼200 °C is attributed to the increase of absorbance (CTTS absorption band) of I⁻ anion at 248 nm with increasing temperature.     

Spectroscopic investigation of laser–water interaction beyond the breakdown threshold energy

The interaction between ns-laser pulse at 532 nm and water, or heavy water (deuterium dioxide), has been studied by Stimulated Raman Scattering (SRS) and optical emission spectroscopy. Both the photolysis and breakdown processes have been considered. When the photolysis is the main process, structural change in water occurs as a consequence of electron and proton hydration. The rearrangement of the water structure and the subsequent photon absorption by free electrons raising the breakdown threshold occur. Moreover, charge separation in bulk water, under laser induced electromagnetic field, leads to a notable enhancement of the SRS signal. On the other hand, for a high laser pulse energy density, electrons gain energy enough to escape from the hydrating water structure, generating electron impact dominated plasma.     

Mechanism of laser-induced size-reduction of gold nanoparticles as studied by nanosecond transient absorption spectroscopy

Gold nanoparticles with an average diameter of approximately 8 nm (Au approximately 15,000) were irradiated with a tightly focused pulse laser at 355 nm in an aqueous solution of sodium dodecyl sulfate (SDS). Transient absorption spectra of the solution were measured at 25-100 ns after the laser irradiation. The observed transient absorption around 720 nm is assignable to the 2p <-- 1s transition of solvated electrons produced via multiple ionization of the gold nanoparticles. The nascent charge state of the gold nanoparticles was estimated from the transient absorbance. The dependence of the charge state on the SDS concentration shows a gradual increase from approximately +60 to approximately +70 in the 2 x 10(-4) to 3 x 10(-4) M range and an abrupt increase up to approximately +710 at the critical micelle concentration (CMC) of SDS, 8 x 10(-3) M. TEM measurements after laser irradiation reveal that the gold nanoparticles fragment into Au(approximately 1000) at a SDS concentration of 3 x 10(-4) M, whereas they are significantly dissociated into Au(approximately 100) above the CMC. The observed correlation between the nascent charge states and the extent of size reduction of the gold nanoparticles after the laser treatment indicates that the size reduction is caused by the Coulomb explosion of the highly charged gold nanoparticles. The mechanism of laser-induced size reduction is quantitatively discussed based on the liquid drop model.     

Time-resolved spectroscopy at the picosecond laser-triggered electron accelerator ELYSE

ELYSE is a fast kinetics center created for pulse radiolysis with picosecond time-resolution. The facility is a 4–9 MeV electron accelerator using a subpicosecond laser pulse to produce an electron pulse from a Cs₂Te semiconductor photocathode and RF gun technology for the electron acceleration. The pulse duration is around 5 ps at low charge (<2 nC) and high energy (9 MeV), and is under routine conditions 10 ps at higher charge (5 nC) and >8 MeV. The dark current at the target is less than 1% of the pulse photocurrent.Time-resolved absorbance measurements in cells placed in front of the electron beam are achieved using pulsed laser diodes, or a xenon flash lamp as light sources, and photodiodes connected to a 3 GHz transient digitizer or a streak camera (250–800 nm range and 3.7 ps time resolution) as detection instruments. In addition, the synchronization between the laser beam and the electron beam is exploited to measure the absorbance by a pump-probe set-up, the pump being the electron pulse produced by the laser pulse, and the probe being part of the laser beam (120 fs–3 ps) delayed by a variable optical line.     

Solvated electrons in dimethylsulphoxide

The optical absorption spectrum obtained by pulse radiolysis of pure liquid dimethylsulphoxide includes a broad intense band in the near IR with λ_max 1500 nm. This band is assigned to solvated electrons with a half-life of 15 ± 2 nsec. The λ_max of the solvated electron correlates better with dimethylsulphoxide's inability to solvate negative ions than with its dielectric constant, which is 48.     

The influence of laser wavelength and fluence on palladium nanoparticles produced by pulsed laser ablation in deionized water

Homogeneous spherical palladium (Pd) nanoparticles were synthesized by pulsed laser ablation of a solid Pd foil target submerged in deionized water, without the addition of any external chemical surfactant. The influence of laser wavelength (355, 532, and 1064 nm) and fluence (8.92, 12.74, and 19.90 J/cm²) on nucleation, growth, and aggregation of Pd nanoparticles were systematically studied. Microstructural and optical properties of the obtained nanoparticles were studied by field emission transmission electron microscopy (FETEM), energy dispersive X-ray spectroscopy, and UV–vis spectroscopy. FETEM micrographs indicate that the average nanocrystallite sizes are relatively low (3–6 nm) and homogeneous for the particles synthesized at the laser wavelengths of 355 and 532 nm. However, at a laser wavelength of 1064 nm, the average nanocrystallite size is relatively large and inhomogeneous in nature. Moreover, we observe that the mean diameter and production rate of particles increases with an increase in laser fluence. The selected area electron diffraction patterns obtained from isolated Pd nanoparticles show the characteristic diffused electron diffraction rings of polycrystalline materials with a face-centered cubic structure. Absorbance spectrum of the synthesized nanoparticle solution shows a broad absorption band, which corresponds to a typical inter-band transition of a metallic system, indicating the production of pure palladium nanoparticles. The present work provides new insights into the effect of laser wavelength and fluence on the control of size and aggregation of palladium nanoparticles in the liquid medium.     

Evidence for laser-induced formation of solvated electrons in room temperature ionic liquids

The photolytic generation of solvated electrons was observed for the first time in two room temperature ionic liquids (RTILs), trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide (IL) and 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide (IL). A 70 fs UV-pulse was used to excite the RTILs, while the transient response was monitored in the visible and near-infrared spectral regions. Immediately after excitation, a pulse duration limited rise of the induced absorption indicated the formation of solvated electrons suggesting the existence of pre-formed traps in RTILs. A broad transient absorption spectrum with a full width at half maximum of about 0.9 eV, typical for solvated electrons, was reconstructed from the transient profiles. Wavelength-independent relaxation dynamics at longer delay times suggest a lifetime of solvated electrons in the ns regime in agreement with results from pulse radiolysis studies. Adding 1,1-dimethylpyrrolidinium iodide to IL led to an increase of the UV absorbance and consequently, to an increase of the yield of solvated electrons. Furthermore, this solute is an efficient electron scavenger causing the transients to decay within about 40 ps.     

Studies of Silver Nanoparticles by Laser Ablation Method

The laser ablation technique has been employed to study silver colloidal formation. Laser intensities, irradiation wavelengths (1064 nm and 532 nm), and solvents (water, methanol, and isopropanol) were all considered. Changes of the maximum UV-Visible absorbance of the solutions with laser intensities exhibited nonlinear behavior for 1064 nm and 532 nm and displayed better ablation efficiency at 532 nm. Larger mean sizes were observed at 532 nm or at higher pulse energy. For solvent effect, the bigger particle sizes were generated in H₂O. As to colloidal stability, isopropanol, which has a lower dielectric constant than water, was found to stabilize Ag nanoparticles without protecting reagents over six months. Preliminary results in 2-butanol suggested that the viscosity of solvent may need to be considered in addition to the dielectric constant.     

HYDRATED ELECTRON FORMATION IN NANOSECOND and PICOSECOND LASER FLASH PHOTOLYSIS OF HEMATOPORPHYRIN IN AQUEOUS SOLUTION

Nanosecond (lambda exc = 266, 355 and 532 nm) and picosecond (lambda exc = 355 nm) laser flash photolysis of hematoporphyrin (Hp) was performed in neutral (pH 7.4) and alkaline (pH 12) aqueous solution, as well as in the presence of 0.1% Triton X-100. The dependence of the yield of photoproduced hydrated electrons (e-aq) on laser pulse energy was studied over a wide range of energies (0.2 to greater than 1000 mJ cm-2). The results show that e-aq are predominantly formed in a two-photon process at lambda exc = 266 and 355 nm. One-photon quantum yields are higher at lambda exc = 266 nm than at lambda exc = 355 nm. Both one-photon and two-photon pathways are less efficient at higher Hp concentration, reflecting the influence of Hp self-aggregation. Two-photon e-aq formation is more efficient when 30 ps pulses are used for excitation, as compared to 10 ns pulses. No e-aq could be detected at lambda exc = 532 nm. Nanosecond pulse-induced transient spectra obtained at pH 7.4 are also discussed.     

Ultrafast dynamics of room temperature ionic liquids after ultraviolet femtosecond excitation

The photochemistry and relaxation dynamics of four room-temperature ionic liquids (RTILs) after ultraviolet (UV) photolysis were investigated by femtosecond pump-probe absorption spectroscopy. A pulse duration-limited rise of the induced absorption in halide-containing RTILs at various probe wavelengths was attributed to the generation of solvated electrons. With continuous irradiation (static conditions), di- and trihalide ion formation became apparent especially below 1000 nm. The formation of trihalide ions was further confirmed by steady-state UV absorption spectroscopy. All RTILs showed a rich photochemistry after UV photolysis leading to the build-up of various long-lived intermediate products as evidenced from the observation that ionic liquids turn yellow upon continuous irradiation. On the other hand, exposing RTILs to the excitation pulse for a short time (rapid-scan method) significantly suppressed the formation of halides. The results suggest that the development of flow-cell systems for highly viscous ionic liquids is urgently needed to quantitatively investigate their ultrafast dynamics.     

Reactivity between biphenyl and precursor of solvated electrons in tetrahydrofuran measured by picosecond pulse radiolysis in near-ultraviolet, visible, and infrared

The initial decrease of solvated electrons in tetrahydrofuran (THF) upon addition of biphenyl was investigated by picosecond pulse radiolysis. Transient absorption spectra derived from the biphenyl radical anion (centered at 408 and 655 nm) and solvated electrons of THF (infrared) were successfully measured in the wavelength region from 400 to 900 nm by the extension of a femtosecond continuum probe light to near-ultraviolet using a second harmonic generation of Ti:sapphire laser and a CaF2 plate. From the analysis of kinetic traces at 1300 nm considering the overlap of primary solvated electrons and partial biphenyl radical anion, C37, which is defined by the solute concentration to reduce the initial yield of solvated electrons to 1/e, was found to be 87 +/- 3 mM. The rate constant of solvated electrons with biphenyl was determined as 5.8 +/- 0.3 x 10(10) M(-1) s(-1). We demonstrate that the kinetic traces at both 408 nm mainly due to biphenyl radical anion and 1300 nm mainly due to solvated electrons are reproduced with high accuracy and consistency by a simple kinetic analysis. Much higher concentrations of biphenyl (up to 2 M) were examined, showing further increase of the initial yield of biphenyl radical anion accompanying a fast decay component. This observation is discussed in terms of geminate ion recombination, scavenging, delayed geminate ion recombination, and direct ionization of biphenyl at high concentration.     

Magnification in excess of 100-times of the microscopic photothermal lensing signal from solute molecules by two-color excitation with continuous-wave lasers.

A microscopic photothermal lensing measurement under two-color continuous-wave laser excitation was performed to investigate a signal enhancement owing to the transient absorption by photoexcited solute molecules in liquid solutions. An intensity-modulated 409 nm laser beam and an un-modulated 532 nm laser beam were used for excitation, and a 670 nm probe beam was used for detecting the modulation amplitude of thermal lensing signals generated with a microscopic objective lens focusing laser beams into a capillary flow cell of 0.1 mm optical path length. The amplitude of the modulated signal increased as the power of the un-modulated laser beam increased, and a 143-times magnification was observed for an iso-propanol solution of naphthacene having 4.6 x 10(-4) absorbance at 409 nm and a negligible absorbance at 532 nm. A four-level model explaining the signal enhancement is proposed, and an important role of the transient absorption by photoexcited molecules is discussed.     

Shallow and deep trap states of solvated electrons in methanol and their formation,electronic excitation,and relaxation dynamics

We present condensed-phase first-principles molecular dynamics simulations to elucidate the presence of different electron trapping sites in liquid methanol and their roles in the formation, electronic transitions, and relaxation of solvated electrons (e_met⁻) in methanol. Excess electrons injected into liquid methanol are most likely trapped by methyl groups, but rapidly diffuse to more stable trapping sites with dangling OH bonds. After localization at the sites with one free OH bond (1OH trapping sites), reorientation of other methanol molecules increases the OH coordination number and the trap depth, and ultimately four OH bonds become coordinated with the excess electrons under thermal conditions. The simulation identified four distinct trapping states with different OH coordination numbers. The simulation results also revealed that electronic transitions of e_met⁻ are primarily due to charge transfer between electron trapping sites (cavities) formed by OH and methyl groups, and that these transitions differ from hydrogenic electronic transitions involving aqueous solvated electrons (e_aq⁻). Such charge transfer also explains the alkyl-chain-length dependence of the photoabsorption peak wavelength and the excited-state lifetime of solvated electrons in primary alcohols.

Condensed-phase first-principles molecular dynamics simulations elucidate the presence of different electron trapping sites in liquid methanol and their roles in the formation, electronic transitions, and relaxation of solvated electrons.     

Spectroscopic study of laser-induced phase transition of gold nanoparticles on nanosecond time scales and longer

The pulsed laser induced phase transition of gold nanoparticles in aqueous solution was observed via a transient absorption on nanosecond time scales and longer. Gold nanoparticles were excited with an intense picosecond laser pulse (355 nm, 30 ps), and the subsequent changes were monitored using two continuous wave laser wavelengths (488 and 635 nm). On the nanosecond time scale, below 6.3 mJ cm(-2), no change was observed; however, in the low fluence region between 6.3 and 17 mJ cm(-2), gold nanoparticles produced a bleach signal (488 nm) attributed to the melting of the gold nanoparticles, which decreased linearly with increasing laser fluence. Laser fluences above 17 mJ cm(-2) resulted in a strong absorption at both wavelengths, which is ascribed to vaporization of gold nanoparticles rather than solvated electrons (ejected from gold nanoparticles) or light scattering. The decay of both signals was faster than the 5 ns time resolution used in our experimental system. On the microsecond time scale, increase in absorbance at 635 nm was observed with a time constant of 1.0 micros, while no change was observed at 488 nm. It is considered that this increase is attributed to the formation of smaller gold nanoparticles resulting from pulsed laser induced size reduction of initial gold nanoparticles.     

DEPENDENCY OF PHOTON DENSITY ON PRIMARY PROCESS OF CATTLE RHODOPSIN

The primary photochemical reactions of cattle rhodopsin suspended in H2O or D2O were compared between excitation with both a weak and an intense picosecond laser pulse (wavelength, 532 nm; duration, 25 ps) at room temperature. The time-dependent change of absorbance at about 575 nm demonstrated that photohodopsin, a precursor of bathorhodopsin, was produced immediately after the excitation with a weak picosecond laser pulse. It decayed to bathorhodopsin with a time constant of 45 ps which is close to the value reported previously [Shichida et al., (1984) Photobiochem. Photobiophys., 7, 221-228]. No deuterium effect was observed in this process. Excitation with an intense laser pulse induced instantaneous increase of the absorbance at about 575 nm and remained at almost constant level on the picosecond time scale, which was in good agreement with the pioneering work [Busch et al., (1972) Proc. Natl. Acad. Sci., USA, 69, 2802-2806]. No deuterium effect was observed in this photochemical process.     

Pulse radiolysis study of the formation and the reactivity of baicalin radical anion,and in comparison with rutin,quercetin and acyrlate ester radical anions in ethanol

The reaction of solvated electrons with baicalin in N₂-saturated ethanol has been studied by pulse radiolysis. The results show that a solvated electron can add to baicalin and generate a baicalin radical anion with a maximum UV absorbance peak at 360 nm. Its molar extinction coefficient at this wavelength is 1.3×10⁴ M⁻¹ cm⁻¹. The rate constant for the build-up of the baicalin radical anion is 1.3(±0.4)×10¹⁰ M⁻¹ s⁻¹. Decay of the radical anion is induced by a proton transfer reaction and a recombination reaction, which involves a pseudo-first-order reaction with rate constant 2.6(±0.4)×10³ s⁻¹ and a second-order reaction with rate constant 1.3(±0.2)×10⁹ M⁻¹ s⁻¹. The effect of acetaldehyde on the decay of the baicalin radical anion was also investigated. Electron transfer between the baicalin radical anion and acetaldehyde was not observed, probably due to the low rate of electron transfer between the baicalin radical anion and acetaldehyde. Reactivity of the rutin, quercetin, baicalin and ethyl acrylate radical anions are also compared.     

Solvation dynamics of electron produced by two-photon ionization of liquid polyols. III. Glycerol

The solvation dynamics of excess electrons in glycerol have been measured by the pump-probe femtosecond laser technique at 333 K. The electrons are produced by two-photon absorption at 263 nm. The change in the induced absorbance is followed up to 450 ps in the spectral range from 440 to 720 nm. The transient signals of electron solvation have been analyzed by two kinetic models: a stepwise mechanism and a continuous relaxation model, using a Bayesian data analysis method. The results are compared with those previously published for ethylene glycol (J. Phys. Chem. A 2006, 110, 175) and for propanediols (J. Phys. Chem. A 2007, 111, 4902). From the comparison, it is pointed out that solvation dynamics in glycerol is very fast despite its high viscosity. This is interpreted as the existence of efficient traps for the electrons in glycerol with low potential energy. The small shift of the absorption band of the excess electron indicates that the potential of these traps is very close to that corresponding to the fully solvated electron.     

One-photon photodetachment of I- in glycerol: spectra and yield of solvated electrons in the temperature range 329<or=T<or=536 K

Solvated electrons in glycerol were generated via a resonant one-photon photodetachment of the charge-transfer-to-solvent (CTTS) band of I- in glycerol (Gl) after irradiation with a 248 nm excimer laser. Optical absorption spectra of solvated electrons (esolv-) in Gl were recorded as a function of temperature (381相似文献