Femtosecond Probe Pulse Research Articles

Time-Resolved Photoelectron Angular Distributions from Strong-Field Ionization of Rotating Naphthalene Molecules

A nanosecond laser pulse confines the spatial orientation of naphthalene in 1D or 3D while a femtosecond kick pulse initiates rotation of the molecular plane around the fixed long axis. Time-dependent photoelectron angular distributions (PADs), resulting from ionization by an intense femtosecond probe pulse, exhibit pronounced changes as the molecular plane rotates. Enhanced 3D alignment, occurring shortly after the kick pulse, provides strongly improved contrast in molecular-frame PADs. Calculations in the strong-field approximation show that the striking structures observed in the PADs originate from nodal planes in occupied valence orbitals.

Lorentzian Amplitude and Phase Pulse Shaping for Nonresonant Background Suppression and Enhanced Spectral Resolution in Coherent Anti-Stokes Raman Scattering Spectroscopy and Microscopy

Femtosecond coherent anti-Stokes Raman scattering (CARS) spectroscopy offers several advantages over spontaneous Raman spectroscopy due to the inherently high sensitivity and low average power deposition in the sample. Femtosecond CARS can be implemented in a collinear pump/probe beam configuration for microspectroscopy applications and has emerged as a powerful technique for chemical imaging of biological specimens. However, one serious limitation of this approach is the presence of a high nonresonant background component that often obscures the resonant signals of interest. We report here an innovative pulse-shaping method based on Lorentzian amplitude and phase spectral modulation of a broadband femtosecond probe pulse that yields spectra with both high spectral resolution and no nonresonant background. No further mathematical analysis is needed to extract Raman spectra. The utility of the proposed method for CARS microscopy is demonstrated using a mixture of polystyrene and latex beads, as well as dry-fixed embryonic stem cells.

Time-resolved dynamics in acetonitrile cluster anions (CH3CN)n-

Abstract Excited state dynamics of acetonitrile cluster anions, ( CH 3 CN ) n - , were investigated using time-resolved photoelectron imaging (TRPEI) for 20 ⩽ n ⩽ 50. The clusters were excited and then photodetached with femtosecond pump and probe pulses at 790 and 395 nm, respectively. Excited state lifetimes varied between 200 and 270 fs over this size range, showing no obvious size trend. Experimental evidence indicates that we are exciting ‘isomer II’ clusters in which the excess electron is valence-bound to a solvated anionic dimer core. The absence of an obvious size-dependence in the excited state lifetimes is consistent with such a structure.

Probing H2 autoionizing states with femto- and attosecond laser pulses

We show the relevance that molecular autoionizing states display in some recent experiments related to the symmetry-breaking in molecular-frame photoelectron angular distributions in H2 when exposed to intense xuv femtosecond laser pulses, and others related to the electron (proton) localization when subject to attosecond pump-probe laser schemes. Our theoretical method solves the time-dependent Schrödinger equation with an spectral method that expands the wave function in terms of H2 correlated stationary vibronic states including all electronic and vibrational degrees of motion. Time-resolved asymmetric electron angular distributions are obtained at specific proton kinetic energies due to the delayed autoionization from H2 doubly excited states, which induces interferences between gerade (1sσg) and ungerade (2pσu) ionization channels. We also study photoionization of H2 exposed to a xuv attosecond pump pulse plus a time-delayed IR femtosecond probe pulse. Fast alternating asymmetries in the proton ejection (electron localization) are obtained as a function of the time delay between the pump and the probe pulses. Finally, we deal with the process of (xuv) two-photon double ionization of H2 under the assumption of having both sequential and non-sequential absorption processes.

Spectral mapping of the third-order optical nonlinearity of glass-metal nanocomposites

By tuning wavelengths of the femtosecond pump and probe pulses we mapped the nonlinear absorption of copper-glass nanocomposites within 520-620 nm range. At the pump intensity of 3 GW/cm(2), the induced transmission rise was as high as 20%. The imaginary part of the third-order optical susceptibility of the nanocomposites as a function of the probe wavelength reproduced well the spectral profile of the surface plasmon resonance in copper. In contrast, the imaginary part of the third-order optical susceptibility as a function of the pump wavelength did not reproduce the plasmon profile being wider than the latter.

Control of femtosecond filamentation by field-free revivals of molecular alignment

We show that the filamentation dynamics of a femtosecond laser probe pulse can be readily controlled by properly matching it to the quantum revivals of pre-aligned molecules prepared through impulsive rotational Raman excitation with an advancing ultrashort pump pulse. Several features of the filamentation process including supercontinuum generation, the length of the plasma channel generated in the wake of the filament, the associated secondary radiations and the multiple filamentation pattern are all easily modified by tuning the cross phase modulation induced by the field-free revivals of molecular alignment, through the delay between the pump and the probe pulses. We show that molecular alignment can also be used to generate conical waves with extremely short intensity spike called shocked X-waves and to further tune the frequency of a few-cycle laser pulse in the wake of a self-guided intense filament.

Broadband sensitive pump-probe setup for ultrafast optical switching of photonic nanostructures and semiconductors

We describe an ultrafast time resolved pump-probe spectroscopy setup aimed at studying the switching of nanophotonic structures. Both femtosecond pump and probe pulses can be independently tuned over broad frequency range between 3850 and 21,050 cm(-1). A broad pump scan range allows a large optical penetration depth, while a broad probe scan range is crucial to study strongly photonic crystals. A new data acquisition method allows for sensitive pump-probe measurements, and corrects for fluctuations in probe intensity and pump stray light. We observe a tenfold improvement of the precision of the setup compared to laser fluctuations, allowing a measurement accuracy of better than DeltaR=0.07% in a 1 s measurement time. Demonstrations of the improved technique are presented for a bulk Si wafer, a three-dimensional Si inverse opal photonic bandgap crystal, and z-scan measurements of the two-photon absorption coefficient of Si, GaAs, and the three-photon absorption coefficient of GaP in the infrared wavelength range.

Spectral modulation of femtosecond laser pulse induced by molecular alignment revivals

We demonstrate experimentally and numerically that the quantum wake of molecular alignment induced by impulsive rotational Raman excitations with femtosecond pump pulses produces observable phase modulations on femtosecond probe pulses. This leads to a spectral red- or blueshift of the probe pulses when they are properly delayed around the rising or falling edge of the half-revival time of the molecular alignment, respectively.

Polarization separator created by a filament in air

We demonstrate that a femtosecond laser pulse-induced filament can act as a "polarization separator" for a copropagating femtosecond probe pulse. The probe component with polarization parallel to the pump is guided along the propagation axis through the cross interactions with the pump pulse. And the probe component with polarization orthogonal to that of the pump is diffracted out into an outer ring by the plasma. The extinction ratio (I(probe)(min) / I(probe)(max)) along the propagation axis is better than 1:20.

Femtosecond Raman‐induced Kerr effect spectroscopy

AbstractWe report the development of a new vibrational technique called Femtosecond Raman‐Induced Kerr Effect Spectroscopy (FRIKES). This technique combines a narrow‐bandwidth picosecond Raman pump pulse with a broadband femtosecond probe pulse to produce high‐resolution Raman‐induced Kerr effect spectra spanning a large vibrational range. Because it is a polarization detection technique, FRIKES produces background‐free Raman spectra with high signal‐to‐noise and rapid acquisition times. The practicality of FRIKES is demonstrated by obtaining Raman spectra of common solvents, revealing that its performance is comparable to femtosecond stimulated Raman spectroscopy (FSRS). The capabilities of FRIKES will make it a valuable new vibrational spectroscopic tool for studies of chemical and biological systems, especially once it is extended to time‐resolved studies. Copyright © 2008 John Wiley & Sons, Ltd.

Origin of negative and dispersive features in anti-Stokes and resonance femtosecond stimulated Raman spectroscopy

Femtosecond stimulated Raman spectroscopy is extended to probe ground state anti-Stokes vibrational features. Off resonance, negative anti-Stokes features are seen that are the mirror image of the positive Stokes side spectra. On resonance, the observed dispersive lineshapes are dramatically dependent on the frequencies of the picosecond pump and femtosecond probe pulses used to generate the stimulated Raman spectra. These observations are explained by the contributions of the inverse Raman and hot luminescence four-wave mixing processes discussed by Sun et al. [J. Chem. Phys. 128, 144114 (2008)], which contribute to the overall femtosecond stimulated Raman signal.

Broadband coherent light generation in diamond driven by femtosecond pulses

We demonstrate broadband light generation in diamond pumped by two-color femtosecond laser pulses. We find that phase matching plays a critical role in the output angle and frequency of the generated sidebands. When a third femtosecond probe pulse is applied to the crystal in the boxed Coherent anti-Stokes Raman Scattering geometry, a two-dimensional array of multi-color beams is generated through the Raman, four-wave mixing, and six-wave-mixing processes. We test the mutual coherence between the generated sidebands. Such coherence, maintained over the broad spectrum, opens possibilities for synthesis of subfemtosecond light waveforms.

Three‐state model for femtosecond broadband stimulated Raman scattering

AbstractStimulated Raman scattering (SRS) is analyzed with a three‐state model. Using a diagrammatic density‐matrix formalism, SRS by a pair of Raman pump and probe pulses, with observation along the probe direction, is described principally by eight terms. The eight terms can be grouped into four sets, which are labeled as SRS or IRS (inverse Raman scattering): SRS(I), SRS(II), IRS(I), and IRS(II). Specializing to the case of femtosecond SRS (FSRS) by a picosecond (ps) Raman pump pulse and a femtosecond (fs) probe pulse, the spectra for the four sets of terms under off‐resonance and resonance conditions were calculated. The results obtained can explain the FSRS experimental observations from a (decaying) stationary vibrational state, such as (1) high wavenumber resolution (determined by the narrow bandwidth Raman pump pulse) and high time resolution (determined by the fs probe pulse), (2) Stokes gain vs anti‐Stokes loss in off‐resonance FSRS, and (3) dispersive lineshapes in resonance FSRS. Copyright © 2008 John Wiley & Sons, Ltd.

Ultrafast temperature jump in liquid water studied by a novel infrared pump-x-ray probe technique

We report the first infrared pump-x-ray probe study of the structural dynamics of liquid water. Femtosecond infrared excitation via the O–H stretching band induces an ultrafast temperature jump that gives rise to changes in the hydrogen bond network. Such changes are probed via the transient x-ray absorption at the oxygen K edge using 70 ps x-ray pulses from a storage ring source. We measure spectra and time evolution of the transient x-ray absorption and calibrate the absolute change of temperature. Our work paves the way for future studies with femtosecond x-ray probe pulses.

Quantum theory of (femtosecond) time-resolved stimulated Raman scattering

We present a complete perturbation theory of stimulated Raman scattering (SRS), which includes the new experimental technique of femtosecond stimulated Raman scattering (FSRS), where a picosecond Raman pump pulse and a femtosecond probe pulse simultaneously act on a stationary or nonstationary vibrational state. It is shown that eight terms in perturbation theory are required to account for SRS, with observation along the probe pulse direction, and they can be grouped into four nonlinear processes which are labeled as stimulated Raman scattering or inverse Raman scattering (IRS): SRS(I), SRS(II), IRS(I), and IRS(II). Previous FSRS theories have used only the SRS(I) process or only the "resonance Raman scattering" term in SRS(I). Each process can be represented by an overlap between a wave packet in the initial electronic state and a wave packet in the excited Raman electronic state. Calculations were performed with Gaussian Raman pump and probe pulses on displaced harmonic potentials to illustrate various features of FSRS, such as high time and frequency resolution; Raman gain for the Stokes line, Raman loss for the anti-Stokes line, and absence of the Rayleigh line in off-resonance FSRS from a stationary or decaying v=0 state; dispersive line shapes in resonance FSRS; and the possibility of observing vibrational wave packet motion with off-resonance FSRS.

Simultaneous time and frequency detection in femtosecond coherent Raman spectroscopy. II. Application to acetonitrile

The preceding paper showed that, in principle, a high-resolution coherent Raman spectrum can be recovered using femtosecond probe pulses by combined detection in both time and frequency. This measurement is possible even when the pulses are too broad in frequency for conventional frequency-domain spectroscopy and too broad in time for conventional time-domain spectroscopy. In this paper, the method is tested on experimental coherent anti-stokes Raman spectroscopy data from acetonitrile. Compared to theoretical models, experimental data are complicated by noise and incomplete knowledge of the pulse structure. Despite these complications, most of the information in the Raman spectrum is recovered from the data: weak transitions are detected and natural-linewidth resolution is achieved across an 800 cm(-1) spectral range. However, circumstances in which experimental limitations result in missed features or ambiguities in the recovered spectrum are also identified. These results suggest where improvements in measurement and data analysis can be made.

Wave packet theory of dynamic stimulated Raman spectra in femtosecond pump-probe spectroscopy

The quantum theory for stimulated Raman spectroscopy from a moving wave packet using the third-order density matrix and polarization is derived. The theory applies, in particular, to the new technique of femtosecond broadband stimulated Raman spectroscopy (FSRS). In the general case, a femtosecond actinic pump pulse first prepares a moving wave packet on an excited state surface which is then interrogated with a coupled pair of picosecond Raman pump pulse and a femtosecond Raman probe pulse and the Raman gain in the direction of the probe pulse is measured. It is shown that the third-order polarization in the time domain, whose Fourier transform governs the Raman gain, is given simply by the overlap of a first-order wave packet created by the Raman pump on the upper electronic state with a second-order wave packet on the initial electronic state that is created by the coupling of the Raman pump and probe fields acting on the molecule. Calculations are performed on model potentials to illustrate and interpret the FSRS spectra.

Complete characterization of molecular vibration using frequency resolved gating

The authors propose a new approach to vibration spectroscopy based on the coherent anti-Stokes Raman scattering of broadband ultrashort laser pulses. The proposed method reveals both the amplitude and the phase of molecular vibrations by utilizing the cross-correlation frequency resolved optical gating (XFROG) technique. The spectrum of the anti-Stokes pulse is measured as a function of the time delay between the laser-induced molecular vibrations and a well characterized broadband femtosecond probe pulse. The iterative XFROG algorithm provides a simultaneous complete characterization of molecular vibrations both in frequency and time domains with high resolution. They demonstrate experimentally the feasibility of the proposed method and show one of its potential applications in disentangling the time behavior of a mixture of vibrationally excited molecules. The technique of femtosecond pulse shaping is used for further improvement of accuracy and stability against noise.

Irreversible Organic Crystalline Chemistry Monitored in Real Time

Because multiple laser shots are typically required to monitor ultrafast photochemical reaction dynamics, sample depletion and product accumulation have greatly restricted the range of substrates and structural environments amenable to study. By implementing a two-dimensional spatial delay gradient across the profile of a femtosecond probe pulse, we can monitor in a single laser shot organic crystalline reaction dynamics despite the formation of permanent photoproducts that cannot be conveniently removed. We monitored the photolysis of the triiodide anion, I3-, and subsequent recombination or relaxation of its reaction products, in three very different pure organic molecular crystals. The experimental results and associated molecular dynamics simulations illustrate the intimate connection between lattice structure and reaction dynamics, highlighting the role of lattice constraints in directing phase-coherent geminate recombination of photofragments within a crystalline reaction cage.

Two-photon excitation of low-lying electronic quadrupole states in atomic clusters

A simple scheme of population and detection of low-lying electronic quadrupole modes in free small deformed metal clusters is proposed. The scheme is analyzed in terms of the time-dependent local density approximation calculations. As a test case, the deformed cluster $\mathrm{Na}_{11}{}^{+}$ is considered. Long-living quadrupole oscillations are generated via resonant two-photon (two-dipole) excitation and then detected through the appearance of satellites in the photoelectron spectra generated by a probe pulse. Femtosecond pump and probe pulses with intensities $I=2\ifmmode\times\else\texttimes\fi{}{10}^{10}--2\ifmmode\times\else\texttimes\fi{}{10}^{11}\phantom{\rule{0.3em}{0ex}}\mathrm{W}∕{\mathrm{cm}}^{2}$ and pulse duration $T=200--500\phantom{\rule{0.3em}{0ex}}\mathrm{fs}$ are found to be optimal. The modes of interest are dominated by a single electron-hole pair and so their energies, being combined with the photoelectron data for hole states, allow us to gather full mean-field spectra of valence electrons near the Fermi energy. Besides, the scheme allows us to estimate the lifetime of electron-hole pairs and hence the relaxation time of electronic energy into ionic heat.