Continuum Probe Research Articles

Correction for the time dependent inner filter effect caused by transient absorption in femtosecond stimulated Raman experiment

Femtosecond stimulated Raman spectroscopy (FSRS) is a promising multiple-pulse ultrafast spectroscopic tool whose simplest form utilizes an actinic pump, a Raman pump and a continuum probe. Here, we report that the transient absorption generated by the actinic pulse modulates the overall magnitude of the Raman signals of the photoactivated sample. As a consequence, the traditional transient FSRS signal is distorted by artifacts, which were observed in the past but left without interpretation. We propose a simple model to calculate the correct transient FSRS signals from the knowledge of transient absorption signal. The model was verified by application to experimental data.

Toward Broad Bandwidth 2-D Electronic Spectroscopy: Correction of Chirp From a Continuum Probe

Recent implementations of 2-D spectroscopy in the pump-probe geometry using a pulse-shaper demonstrate the ease with which frequency-resolved pump-probe experiments can be readily adapted to 2-D methods. Many frequency-resolved pump-probe experiments employ continuum probes to observe a broad range of electronic transitions. These continuum probes are often chirped, leading to distortions that can be post corrected by characterizing the chirp and appropriately adjusting the observed wavelength-dependent pump-probe time delay. We present an analogous chirp-correction scheme for 2-D spectroscopy, facilitating the use of continuum probing to expand the frequency information available in 2-D spectroscopy experiments. We demonstrate the method through experiments and simulations of a laser dye in solution.

Relaxation dynamics of Au25L18 nanoclusters studied by femtosecond time-resolved near infrared transient absorption spectroscopy

The relaxation dynamics of electronically excited [Au(25)(SR)(18)](q), where q = 0 or -1 and SR = S(CH(2))(2)Ph, were studied using femtosecond time-resolved transient absorption spectroscopy. Nanoclusters excited by 400 nm light were probed using temporally delayed broad-bandwidth continuum probe pulses. Continuum pulses were generated in both the visible and near infrared (NIR) spectral regions, providing access to a wide range of transient spectral features. The use of NIR probe pulses allowed the relaxation dynamics of the excited states located near the HOMO-LUMO energy gap to be monitored in the probe step via the sp ← LUMO and sp ← LUMO+1 transitions. These NIR measurements yielded excited state absorption (ESA) data that were much less congested than the typical visible transient spectrum. For the neutral nanocluster, the time-domain data were composed of three components: (1) a few-picosecond decay, (2) a slower decay taking a few hundred picoseconds and (3) a non-decaying plateau function. Component 1 reflected energy relaxation to semi-ring ligand states; component 2 was attributed to relaxation via a manifold of states located near the HOMO-LUMO energy gap. Component 3 arose from slow radiative recombination. The dynamics of the anion depended upon the identity of the excited state from which the particle was relaxing. The LUMO+1 state of the anion exhibited relaxation dynamics that were similar to those observed for the neutral nanocluster. By comparison, the time-domain data observed for the LUMO state contained only two components: (1) a 3.3 ± 0.2 ps decay and (2) a 5 ± 1 ns decay. The amplitude coefficients of each component were also analyzed. Taken together, the amplitude coefficients and lifetimes were indicative of an activation barrier located approximately 100 meV above the HOMO-LUMO energy gap, which mediated a previously unobserved excited state decay process for [Au(25)(SR)(18)](0). These data suggested that NIR ESA measurements will be instrumental in describing the relaxation processes of quantum-confined nanoclusters.

Dynamics and Transient Absorption Spectral Signatures of the Single-Wall Carbon Nanotube Electronically Excited Triplet State

We utilize femtosecond-to-microsecond time domain pump-probe transient absorption spectroscopy to interrogate for the first time the electronically excited triplet state of individualized single-wall carbon nanotubes (SWNTs). These studies exploit (6,5) chirality-enriched SWNT samples and poly[2,6-{1,5-bis(3-propoxysulfonic acid sodium salt)}naphthylene]ethynylene (PNES), which helically wraps the nanotube surface with periodic and constant morphology (pitch length = 10 ± 2 nm), providing a self-assembled superstructure that maintains structural homogeneity in multiple solvents. Spectroscopic interrogation of such PNES-SWNT samples in aqueous and DMSO solvents using E(22) excitation and a white-light continuum probe enables E(11) and E(22) spectral evolution to be monitored concomitantly. Such experiments not only reveal classic SWNT singlet exciton relaxation dynamics and transient absorption signatures but also demonstrate spectral evolution consistent with formation of a triplet exciton state. Transient dynamical studies evince that (6,5) SWNTs exhibit rapid S(1)→T(1) intersystem crossing (ISC) (τ(ISC) ~20 ps), a sharp T(1)→T(n) transient absorption signal (λ(max)(T(1)→T(n)) = 1150 nm; full width at half-maximum ≈ 350 cm(-1)), and a substantial T(1) excited-state lifetime (τ(es) ≈ 15 μs). Consistent with expectations for a triplet exciton state, T(1)-state spectral signatures and T(1)-state formation and decay dynamics for PNES-SWNTs in aqueous and DMSO solvents, as well as those determined for benchmark sodium cholate suspensions of (6,5) SWNTs, are similar; likewise, studies that probe the (3)[(6,5) SWNT]* state in air-saturated solutions demonstrate (3)O(2) quenching dynamics reminiscent of those determined for conjugated aromatic hydrocarbon excited triplet states.

Femtosecond carrier dynamics in bulk graphite and graphene paper

Femtosecond white-light continuum probe transient absorption and reflectivity measurements of bulk graphite and graphene paper are reported. In graphite, the relaxation of photoinduced electron–hole pairs happens through in-plane electron–electron and electron–phonon scattering in ≃200fs, while the ps dynamics is due to the modulation of the electronic structure by out-of-plane structural motions. The ps dynamics of the optical signal is strongly reduced in graphene paper, where the out-of-plane bond is disrupted, while the short component of the dynamics is identical in both materials. These results show that in 2D-graphene, the carrier relaxation occurs in ≃200fs.

Photodissociation of thioglycolic acid studied by femtosecond time-resolved transient absorption spectroscopy

Steady-state and time-resolved spectroscopies were employed to study the photodissociation of both the neutral (HS-CH(2)-COOH) and doubly deprotonated ((-)S-CH(2)-COO(-)) forms of thioglycolic acid (TGA), a common surface-passivating ligand used in the aqueous synthesis and organization of semiconducting nanostructures. Room temperature UV-Vis absorption spectroscopy indicated strong absorption by the S(1) and S(2) excited states at 250 nm and 185 nm, respectively. The spectrum also contained a weaker absorption band that extended to approximately 550 nm, which was assigned to the π(CO) (*)←n(O) transition. Femtosecond time-resolved transient absorption spectroscopy was performed on TGA using 400 nm excitation and a white-light continuum probe to provide the temporally and spectrally resolved data. Both forms of TGA underwent a photoinduced dissociation from the excited state to form an α-thiol-substituted acyl radical (α-TAR, S-CH(2)-CO(●)). For the acidic form of TGA, radical formation occurred with an apparent time constant of 60 ± 5 fs; subsequent unimolecular decay took 400 ± 60 fs. Similar kinetics were observed for the deprotonated form of TGA (70 ± 10 fs radical formation; 420 ± 40 fs decay). The production of the α-TAR was corroborated by the observation of its characteristic optical absorption. Time-resolved data indicated that the photoinduced dissociation of TGA via cleavage of the C-OH bond occurred rapidly (≤100 fs). The prevalence of TGA in aqueous semiconducting nanoparticles makes its absorption in the visible spectral region and subsequent dissociation key to understanding the behavior of nanoscale systems.

Visualizing coherent phonon propagation in the 100 GHz range: A broadband picosecond acoustics approach

Building on a 1 kHz amplified Ti:sapphire laser source, we developed a novel pump-probe setup for broadband picosecond acoustics using a white-light continuum probe coupled to an optical multichannel analyzer. The system allows one to access, in a single measurement, acoustic parameters such as sound velocity and attenuation all over the bandwidth of the acoustic wave-packet launched by the pump pulse. We use the setup to measure the sound attenuation in fused silica and observe a dynamic crossover occurring at ≈170 GHz.

ChemInform Abstract: New Two-Photon Absorbing Fluorene Derivatives: Synthesis and Nonlinear Optical Characterization.

Efficient Pd-catalyzed Heck coupling methodology was employed to provide two new fluorene derivatives with phosphonate (2) and nitro (3) electron-withdrawing functionalities. Both derivatives exhibit two-photon absorption (2PA), as determined by nonlinear absorption measurements using a femtosecond pump/white light continuum probe “NLO spectrometer”. Both fluorene derivatives have high 2PA cross sections (650 and 1300 × 10-50 cm4 s photon-1 molecule-1 for compounds 2 and 3, respectively).

Heme Ligand Binding Properties and Intradimer Interactions in the Full-length Sensor Protein Dos from Escherichia coli and Its Isolated Heme Domain

Dos from Escherichia coli is a bacterial gas sensor protein comprising a heme-containing gas sensor domain and a phosphodiesterase catalytic domain. Using a combination of static light scattering and gel filtration experiments, we established that, as are many other sensor proteins, the full-length protein is dimeric. The full-length dimer (association constant <10 nm) is more stable than the dimeric heme domain (association constant approximately 1 mum), and the dimer interface presumably includes both sensor and catalytic domains. Ultrafast spectroscopic studies showed little influence of the catalytic domain on kinetic processes in the direct vicinity of the heme. By contrast, the properties of ligand (CO and O(2)) binding to the heme in the sensor domain, occurring on a microsecond to second time scale, were found to be influenced by (i) the presence of the catalytic domain, (ii) the dimerization state, and in dimers, (iii) the ligation state of the other subunit. These results imply allosteric interactions within dimers. Steady-state titrations demonstrated marked cooperativity in oxygen binding to both the full-length protein and the isolated heme domain, a feature not reported to date for any dimeric sensor protein. Analysis of a variety of time-resolved experiments showed that Met-95 plays a major role in the intradimer interactions. The intrinsic binding and dissociation rates of Met-95 to the heme were modulated approximately 10-fold by intradimer and sensor-catalytic domain interactions. Dimerization effects were also observed for cyanide binding to the ferric heme domains, suggesting a similar role for Met-95 in ferric proteins.

Two-dimensional electronic spectroscopy with a continuum probe

We report 2D Fourier transform electronic spectroscopy obtained in the pump-probe geometry using a continuum probe. An acousto-optic pulse shaper placed in the pump arm of a standard pump-continuum probe experiment permits 2D spectroscopy that probes a broad spectral range. We demonstrate the method on a simple dye system exhibiting vibrational wavepacket dynamics that modulate the peak shapes of the 2D spectra. The broad spectral range of the continuum probe allows us to observe vibronic cross peaks in the 2D spectra.

Effective Two-Photon Absorption Cross Section of Heteroaromatic Quadrupolar Dyes: Dependence on Measurement Technique and Laser Pulse Characteristics

The linear and nonlinear optical properties of the heteroaromatic push-pull-push two-photon absorbing dye N-methyl-2,5-bis[1-(N-methylpyrid-4-yl)ethen-2-yl]-pyrrole ditriflate (PEPEP) are reported. The determination of the two-photon absorption (TPA) cross-section spectrum has been performed with different techniques: femtosecond TPA-white light continuum probe experiments, two-photon-induced fluorescence, and open aperture Z-scan measurements using both nanosecond and femtosecond laser pulses. The measured TPA cross sections and their wavelength dispersion show a marked dependence on the parameters of the laser pulses and on the measurement technique employed. These properties are discussed in terms of the different microscopic mechanisms that can contribute to the multiphoton absorption processes, with different weight depending on the measurement conditions and on the photophysical parameters of the dye.

Ligand Dynamics and Early Signaling Events in the Heme Domain of the Sensor Protein Dos from Escherichia coli

In the heme-based sensor Dos from Escherichia coli, the ferrous heme is coordinated by His-77 and Met-95. The latter residue is replaced upon oxygen binding or oxidation of the heme. Here we investigate the early signaling processes upon dissociation of the distal ligand using ultrafast spectroscopy and site-directed mutagenesis. Geminate CO rebinding to the heme domain DosH appears insensitive to replacement of Met-95, in agreement with the notion that this residue is oriented out of the heme pocket in the presence of external ligands. A uniquely slow 35-ps phase in rebinding of the flexible methionine side chain after dissociation from ferrous DosH is completely abolished in rebinding of the more rigid histidine side chain in the M95H mutant protein, where only the 7-ps phase, common to all 6-coordinate heme proteins, is observed. Temperature-dependence studies indicate that all rebinding of internal and external ligands is essentially barrierless, but that CfigsO escape from the heme pocket is an activated process. Solvent viscosity studies combined with molecular dynamics simulations show that there are two configurations in the ferrous 6-coordinate protein, involving two isomers of the Met-95 side chain, of which the structural changes extend to the solvent-exposed backbone, which is part of the flexible FG loop. One of these configurations has considerable motional freedom in the Met-95-dissociated state. We suggest that this configuration corresponds to an early signaling intermediate state, is responsible for the slow rebinding, and allows small ligands in the protein to efficiently compete for binding with the heme.

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.

Time-resolved spectroscopy of non-thermal carrier dynamics in GaN

Abstract The dynamics of carriers in GaN epilayers is investigated using femtosecond pump-probe spectroscopy. After the residual chirp on the continuum probe is removed, the normalized difference spectra (NDS) for different probe energies are synchronized, recovering the full time resolution of our laser pulse. Our Monte-Carlo simulation agrees well with the unchirped NDS spectrum, which shows the development of the carrier distribution at early times, where phonon satellites are seen, together with a strong non-thermal electron distribution in the region of the LO-phonon energy arising from the remarkably strong electron–LO phonon interaction. Employing a new technique which involves the integration of the normalized NDS multiplied by the corresponding energy, a measure of the mean energy of the carriers in non-thermal states is obtained. By comparing the time-dependent energy loss with the theoretical energy loss rate, we estimate the effective temperature of the phonon modes as well as the population of phonons.

All-optical switching potentiality in Fabry–Perot devices containing poly-DCHD

The linear and nonlinear response of Fabry–Perot etalons containing a polymer microcrystal solution was studied using the pump–probe technique with a white-light continuum probe. The response was studied at wavelengths away from resonance (700–800nm) when a near-resonant subpicosecond pump pulse (at 640nm) was used. A theoretical model used to describe the F–P linear transmission is presented. A blue-shift of the F–P peaks induced by the pump-pulse was clearly observed in all the etalons studied, and the magnitude of the shifts is used to quantify the nonlinear response. The potential of these devices for all-optical switching applications is assessed through the figures of merit W and T, and the recovery time of the nonlinearity. Refractive index changes as large as 1.2×10−2 were measured and switching energies as low as 0.9pJ were calculated at the F–P peaks. The nonlinear response was shown to have an ultrafast recovery, of around 2ps.

Stability of High-Density One-Dimensional Excitons in Carbon Nanotubes under High Laser Excitation

Through ultrafast pump-probe spectroscopy with intense pump pulses and a wide continuum probe, we show that interband exciton peaks in single-walled carbon nanotubes (SWNTs) are extremely stable under high laser excitations. Estimates of the initial densities of excitons from the excitation conditions, combined with recent theoretical calculations of exciton Bohr radii for SWNTs, suggest that their positions do not change at all even near the Mott density. In addition, we found that the presence of lowest-subband excitons broadens all absorption peaks, including those in the second-subband range, which provides a consistent explanation for the complex spectral dependence of pump-probe signals reported for SWNTs.

Strong Enhancement of the Two-Photon Absorption of Tetrakis(4-sulfonatophenyl)porphyrin Diacid in Water upon Aggregation

A strong enhancement of the two-photon absorption (TPA) cross section of tetrakis(4-sulfonatophenyl)porphyrin diacid (H(4)TPPS(2-)) at various wavelengths when a J-type aggregate is formed in water with respect to the one observed for the H(4)TPPS(2-) monomer in a mixture of water, dimethyl sulfoxide (DMSO), and urea is presented. The TPA properties are characterized by the open aperture Z-scan technique and the ultrafast two-photon absorption spectroscopy with white light continuum probe (TPA-WLCP) technique. The observed enhancement is discussed in terms of possible electronic cooperative effects in the aggregate.

Femtosecond broadband stimulated Raman spectroscopy: Apparatus and methods

The laser, detection system, and methods that enable femtosecond broadband stimulated Raman spectroscopy (FSRS) are presented in detail. FSRS is a unique tool for obtaining high time resolution (<100 fs) vibrational spectra with an instrument response limited frequency resolution of <10 cm(-1). A titanium:Sapphire-based laser system produces the three different pulses needed for FSRS: (1) A femtosecond visible actinic pump that initiates the photochemistry, (2) a narrow bandwidth picosecond Raman pump that provides the energy reservoir for amplification of the probe, and (3) a femtosecond continuum probe that is amplified at Raman resonances shifted from the Raman pump. The dependence of the stimulated Raman signal on experimental parameters is explored, demonstrating the expected exponential increase in Raman intensity with concentration, pathlength, and Raman pump power. Raman spectra collected under different electronic resonance conditions using highly fluorescent samples highlight the fluorescence rejection capabilities of FSRS. Data are also presented illustrating our ability: (i) To obtain spectra when there is a large transient absorption change by using a shifted excitation difference technique and (ii) to obtain high time resolution vibrational spectra of transient electronic states.

Photoinduced Intermolecular Electron Transfer in Liquid Solutions

Intermolecular photoinduced electron transfer between Rhodamine 3B cation (R3B+), and dimethylanaline (DMA) is studied in a variety of solvents using pump−probe spectroscopy from ultrashort times (∼100 fs) to long times (∼10 ns). Excitation of R3B+ results in the transfer of an electron from DMA and the production of the neutral radical R3B and the DMA+ radical cation. Using a very broadband continuum probe, the generation of the R3B neutral radical is observed (430 nm) as well as the ground state bleach (550 nm), an excited state absorption (445 nm), and stimulated emission (620 nm). A good spectrum of the R3B radical is obtained by removing the overlapping excited state absorption. The forward electron transfer is examined by monitoring the time dependence of the stimulated emission. The data are analyzed with a previously presented detailed theory of through-solvent electron transfer for diffusing donors and acceptors, which includes the influences solvent structure and the hydrodynamic effect. Previous studies have shown that the theory works well for times >100 ps. It is found that in a non-hydrogen-bonding solvent (acetonitrile) and in mixtures of hydrogen-bonding solvents, the theory works well down to a few hundred femtoseconds with only one adjustable parameter, the contact electronic coupling matrix element. However, in pure hydrogen-bonding solvents, it is necessary to increase the solvent hard sphere radius used in the radial distribution to theoretically describe the data, which suggest a larger solvent structural unit than a single solvent molecule.

Correction to "Experiment and analysis of two-photon absorption spectroscopy using a white-light continuum probe"

Correction to "Experiment and analysis of two-photon absorption spectroscopy using a white-light continuum probe"