Spectral control of high-harmonic generation via drive laser pulse shaping in a wide-diameter capillary.

We experimentally investigate spectral control of high-harmonic generation in a wide-diameter (508 µm) capillary that allows using significantly lower gas pressures coupled with elevated drive laser energies to achieve higher harmonic energies. Using phase shaping to change the linear chirp of the drive laser pulses, we observe wavelength tuning of the high-harmonic output to both larger and smaller values. Comparing tuning via the gas pressure with the amount of blue shift in the transmitted drive laser spectrum, we conclude that both adiabatic and non-adiabatic effects cause pulse-shaping induced tuning of high harmonics. We obtain a fractional wavelength tuning, Δλ/λ, in the range from -0.007 to + 0.01, which is comparable to what is achieved with standard capillaries of smaller diameter and higher pressures.

Single-shot fluctuations in waveguided high-harmonic generation.

For exploring the application potential of coherent soft x-ray (SXR) and extreme ultraviolet radiation (XUV) provided by high-harmonic generation, it is important to characterize the central output parameters. Of specific importance are pulse-to-pulse (shot-to-shot) fluctuations of the high-harmonic output energy, fluctuations of the direction of the emission (pointing instabilities), and fluctuations of the beam divergence and shape that reduce the spatial coherence. We present the first single-shot measurements of waveguided high-harmonic generation in a waveguided (capillary-based) geometry. Using a capillary waveguide filled with Argon gas as the nonlinear medium, we provide the first characterization of shot-to-shot fluctuations of the pulse energy, of the divergence and of the beam pointing. We record the strength of these fluctuations vs. two basic input parameters, which are the drive laser pulse energy and the gas pressure in the capillary waveguide. In correlation measurements between single-shot drive laser beam profiles and single-shot high-harmonic beam profiles we prove the absence of drive laser beam-pointing-induced fluctuations in the high-harmonic output. We attribute the main source of high-harmonic fluctuations to ionization-induced nonlinear mode mixing during propagation of the drive laser pulse inside the capillary waveguide.

Quantum control experiment reveals solvation-induced decoherence.

Coherent control holds the promise of becoming a powerful spectroscopic tool for the study of complex molecular systems. Achieving control requires coherence in the quantum system under study. In the condensed phase, coherence is typically lost rapidly because of fluctuating interactions between the solvated molecule and its surrounding environment. We investigate the degree of attainable control on a dye molecule when the fluctuations of its environment are systematically varied. A single successful learning curve for optimizing stimulated emission from the dye in solution is reapplied for a range of solvents with varying viscosity, revealing a striking trend that is correlated directly with the dephasing time. Our results provide clear evidence that the environment limits the leverage of control on the molecular system. This insight can be used to enhance the yield of control experiments greatly.

The validity of the "diradical" hypothesis: direct femtoscond studies of the transition-state structures.

Direct studies of diradicals, the molecular species hypothesized to be archetypal of chemical bond transformations in many classes of reactions, have been made using femtosecond laser techniques with mass spectrometry in a molecular beam. These studies are aimed at "freezing" the diradicals in time and in the course of the reaction. The passage of these species through the transition-state region was observed and the effect of total energy and alkyl substitution on the rates of bond closure and cleavage was examined. The results establish the nature of these intermediates and define their existence during reactions.

Background free CARS imaging by phase sensitive heterodyne CARS.

In this article we show that heterodyne CARS, based on a controlled and stable phase-preserving chain, can be used to measure amplitude and phase information of molecular vibration modes. The technique is validated by a comparison of the imaginary part of the heterodyne CARS spectrum to the spontaneous Raman spectrum of polyethylene. The detection of the phase allows for rejection of the non-resonant background from the data. The resulting improvement of the signal to noise ratio is shown by measurements on a sample containing lipid.

Application of spectral phase shaping to high resolution CARS spectroscopy.

By spectral phase shaping of both the pump and probe pulses in coherent anti-Stokes Raman scattering (CARS) spectroscopy we demonstrate the extraction of the frequencies, bandwidths and relative cross sections of vibrational lines. We employ a tunable broadband Ti:Sapphire laser synchronized to a ps-Nd:YVO mode locked laser. A high resolution spectral phase shaper allows for spectroscopy with a precision better than 1 cm(-1) in the high frequency region around 3000 cm(-1). We also demonstrate how new spectral phase shaping strategies can amplify the resonant features of isolated vibrations to such an extent that spectroscopy and microscopy can be done at high resolution, on the integrated spectral response without the need for a spectrograph.

Low-noise rotating sample holder for ultrafast transient spectroscopy at cryogenic temperatures.

We present the design and testing of a rotating device that fits within a commercial helium cryostat and is capable of providing at 4 K a fresh sample surface for subsequent shots of a 1-10 kHz amplified pulsed laser. We benchmark this rotator in a transient-absorption experiment on molecular switches. After showing that the device introduces only a small amount of additional noise, we demonstrate how the effect of signal degradation due to high fluence is completely resolved.

Coherent control of vibrational transitions: discriminating molecules in mixtures.

Identifying complex molecules often entails detection of multiple vibrational resonances, especially in the case of mixtures. Phase shaping of broadband pump and probe pulses allows for the coherent superposition of several resonances, such that specific molecules can be detected directly and with high selectivity. Our particular implementation of coherent anti-Stokes Raman scattering (CARS) spectroscopy and imaging employs broadband pump and probe fields in combination with a narrowband Stokes field. We describe our approach for combining spectral phase shaping and closed-loop optimization strategies to perform chemically-selective microscopy. To predict the optimal excitation profile we employ evolutionary algorithms that use the vibrational phase responses of five distinct molecules with overlapping resonances and investigate the effect of phase instability on the optimization. We have recently shown that modified polynomials and orthogonal rational functions can give rise to improved contours for CARS fitness landscapes. Now, by considering the landscapes associated with different basis sets, we introduce two figures of merit to quantitatively rank basis functions in terms of their "appropriateness" for modeling nonlinear phase-shaped processes.

Vibrational phase contrast microscopy by use of coherent anti-Stokes Raman scattering.

In biological samples the resonant coherent anti-Stokes Raman scattering signal of less abundant constituents can be overwhelmed by the nonresonant background, preventing detection of those molecules. We demonstrate a method to obtain the phase of the oscillators in the focal volume that allows discrimination of those hidden molecules. The phase is measured with respect to the local excitation fields using a cascaded phase-preserving chain. It is measured point-by-point and takes into account refractive index changes in the sample, phase curvature over the field-of-view, and interferometric instabilities. The detection of the phase of the vibrational motion can be regarded as a vibrational extension of the linear (refractive index) phase contrast microscopy introduced by Zernike around 1933.

Direct observation of the (forbidden) S1 state in carotenoids.

Carotenoids are involved in a variety of biological functions, yet the underlying mechanisms are poorly understood, in part because of the long-standing difficulty in assigning the location of the first excited (S1) state. Here, we present a method for determining the energy of the forbidden S1 state, on the basis of ultrafast spectroscopy of the short lived level. Femtosecond transient absorption spectra and kinetics of the S1 --> S2 transition revealed the location of the intermediate level in two carotenoid species involved in the xanthophyll cycle, zeaxanthin and violaxanthin, and yielded surprising implications regarding the mechanism of photoregulation in photosynthesis.

Exciton delocalization probed by excitation annihilation in the light-harvesting antenna LH2.

Singlet-singlet annihilation is used to study exciton delocalization in the light harvesting antenna complex LH2 (B800-B850) from the photosynthetic purple bacterium Rhodobacter sphaeroides. The characteristic femtosecond decay constants of the high intensity isotropic and the low intensity anisotropy kinetics of the B850 ring are related to the hopping time tau(h) and the coherence length N(coh) of the exciton. Our analysis yields N(coh) = 2.8+/-0.4 and tau(h) = 0.27+/-0.05 ps. This approach can be seen as an extension to the concept of the spectroscopic ruler.

Dynamics of energy transfer from lycopene to bacteriochlorophyll in genetically-modified LH2 complexes of Rhodobacter sphaeroides.

LH2 complexes from Rb. sphaeroides were modified genetically so that lycopene, with 11 saturated double bonds, replaced the native carotenoids which contain 10 saturated double bonds. Tuning the S1 level of the carotenoid in LH2 in this way affected the dynamics of energy transfer within LH2, which were investigated using both steady-state and time-resolved techniques. The S1 energy of lycopene in n-hexane was determined to be approximately 12 500 +/- 150 cm(-1), by direct measurement of the S1-S2 transient absorption spectrum using a femtosecond IR-probing technique, thus placing an upper limit on the S1 energy of lycopene in the LH2 complex. Fluorescence emission and excitation spectra demonstrated that energy can be transferred from lycopene to the bacteriochlorophyll molecules within this LH2 complex. The energy-transfer dynamics within the mutant complex were compared to wild-type LH2 from Rb. sphaeroides containing the carotenoid spheroidene and from Rs. molischianum, in which lycopene is the native carotenoid. The results show that the overall efficiency for Crt --> B850 energy transfer is approximately 80% in lyco-LH2 and approximately 95% in WT-LH2 of Rb. sphaeroides. The difference in overall Crt --> BChl transfer efficiency of lyco-LH2 and WT-LH2 mainly relates to the low efficiency of the Crt S(1) --> BChl pathway for complexes containing lycopene, which was 20% in lyco-LH2. These results show that in an LH2 complex where the Crt S1 energy is sufficiently high to provide efficient spectral overlap with both B800 and B850 Q(y) states, energy transfer via the Crt S1 state occurs to both pigments. However, the introduction of lycopene into the Rb. sphaeroides LH2 complex lowers the S1 level of the carotenoid sufficiently to prevent efficient transfer of energy to the B800 Q(y) state, leaving only the Crt S1 --> B850 channel, strongly suggesting that Crt S1 --> BChl energy transfer is controlled by the relative Crt S1 and BChl Q(y) energies.

Ultrafast carotenoid band shifts probe structure and dynamics in photosynthetic antenna complexes.

We report observations of ultrafast carotenoid band shifts correlated with energy transfer dynamics between bacteriochlorophyll (BChl) molecules within the peripheral light-harvesting complex (LH2) from the photosynthetic bacterium Rhodobacter sphaeroides. Direct excitation of the bacteriochlorophyll Qy bands yielded distinct changes in the carotenoid S2 absorption from 430 to 530 nm. Transient absorption spectra and kinetics were measured in a femtosecond pump-probe experiment, revealing the ultrafast carotenoid response to excited BChl pigments. These data are an indication of a new property of carotenoids that is manifested as a unique ability to detect and report changes in their immediate environment, thereby serving as sensitive probes of local structure and dynamics.

B800-->B850 energy transfer mechanism in bacterial LH2 complexes investigated by B800 pigment exchange.

Femtosecond transient absorption measurements were performed on native and a series of reconstituted LH2 complexes from Rhodopseudomonas acidophila 10050 at room temperature. The reconstituted complexes contain chemically modified tetrapyrrole pigments in place of the native bacteriochlorophyll a-B800 molecules. The spectral characteristics of the modified pigments vary significantly, such that within the B800 binding sites the B800 Q(y) absorption maximum can be shifted incrementally from 800 to 670 nm. As the spectral overlap between the B800 and B850 Q(y) bands decreases, the rate of energy transfer (as determined by the time-dependent bleaching of the B850 absorption band) also decreases; the measured time constants range from 0.9 ps (bacteriochlorophyll a in the B800 sites, Q(y) absorption maximum at 800 nm) to 8.3 ps (chlorophyll a in the B800 sites, Q(y) absorption maximum at 670 nm). This correlation between energy transfer rate and spectral blue-shift of the B800 absorption band is in qualitative agreement with the trend predicted from Förster spectral overlap calculations, although the experimentally determined rates are approximately 5 times faster than those predicted by simulations. This discrepancy is attributed to an underestimation of the electronic coupling between the B800 and B850 molecules.