Average power scaling of THz spintronic emitters efficiently cooled in reflection geometry.

Metallic spintronic terahertz (THz) emitters have become well-established for offering ultra-broadband, gapless THz emission in a variety of excitation regimes, in combination with reliable fabrication and excellent scalability. However, so far, their potential for high-average-power excitation to reach strong THz fields at high repetition rates has not been thoroughly investigated. In this article, we explore the power scaling behavior of tri-layer spintronic emitters using an Yb-fiber excitation source, delivering an average power of 18.5 W (7 W incident on the emitter after chopping) at 400 kHz repetition rate, temporally compressed to a pulse duration of 27 fs. We confirm that a reflection geometry with back-side cooling is ideally suited for these emitters in the high-average-power excitation regime. In order to understand limiting mechanisms, we disentangle the effects on THz power generation by average power and pulse energy by varying the repetition rate of the laser. Our results show that the conversion efficiency is predominantly determined by the incident fluence in this high-average-power, high-repetition-rate excitation regime if the emitters are efficiently cooled. Using these findings, we optimize the conversion efficiency and reach highest excitation powers in the back-cooled reflection geometry. Our findings provide guidelines for scaling the power of THz radiation emitted by spintronic emitters to the milliwatt-level by using state-of-the-art femtosecond sources with multi-hundred-Watt average power to reach ultra-broadband, strong-field THz sources with high repetition rate.

Directly diode-pumped femtosecond Cr:ZnS amplifier with ultra-low intensity noise.

Diode-pumped Cr:ZnS oscillators have emerged as precursors for single-cycle infrared pulse generation with excellent noise performance. Here we demonstrate a Cr:ZnS amplifier with direct diode-pumping to boost the output of an ultrafast Cr:ZnS oscillator with minimum added intensity noise. Seeded with a 0.66-W pulse train at 50-MHz repetition rate and 2.4 µm center wavelength, the amplifier provides over 2.2 W of 35-fs pulses. Due to the low-noise performance of the laser pump diodes in the relevant frequency range, the amplifier output achieves a root mean square (RMS) intensity noise level of only 0.03% in the 10 Hz-1 MHz frequency range and a long-term power stability of 0.13% RMS over one hour. The diode-pumped amplifier reported here is a promising driving source for nonlinear compression to the single- or sub-cycle regime, as well as for the generation of bright, multi-octave-spanning mid-infrared pulses for ultra-sensitive vibrational spectroscopy.

Ultra-rapid electro-optic sampling of octave-spanning mid-infrared waveforms.

We demonstrate ultra-rapid electro-optic sampling (EOS) of octave-spanning mid-infrared pulses centered at 9 µm, implemented by mechanically scanning a mirror with a sonotrode resonating at 19 kHz (forward and backward acquisition at 38 kHz). The instrument records the infrared waveform with a spectral intensity dynamic range of 1.6 × 105 for a single scan over a 1.6-ps delay range, acquired within 26 µs. The purely reflective nature of the delay scanning technique is compatible with broad optical bandwidths, short pulse durations (16 fs, centered at 1030 nm) and high average powers (Watt-level). Interferometric tracking of the sonotrode motion in combination with a predictor-corrector algorithm allows for delay-axis determination with down to single-digit attosecond precision. Ultra-rapid mid-infrared EOS will advance applications such as molecular fingerprinting of static samples as well as tracking of biological processes and chemical reactions and is likely to find new fields of application such as infrared-spectroscopic flow cytometry.

Primary events in the blue light sensor plant cryptochrome: intraprotein electron and proton transfer revealed by femtosecond spectroscopy.

Photoreceptors are chromoproteins that undergo fast conversion from dark to signaling states upon light absorption by the chromophore. The signaling state starts signal transduction in vivo and elicits a biological response. Therefore, photoreceptors are ideally suited for analysis of protein activation by time-resolved spectroscopy. We focus on plant cryptochromes which are blue light sensors regulating the development and daily rhythm of plants. The signaling state of these flavoproteins is the neutral radical of the flavin chromophore. It forms on the microsecond time scale after light absorption by the oxidized state. We apply here femtosecond broad-band transient absorption to early stages of signaling-state formation in a plant cryptochrome from the green alga Chlamydomonas reinhardtii. Transient spectra show (i) subpicosecond decay of flavin-stimulated emission and (ii) further decay of signal until 100 ps delay with nearly constant spectral shape. The first decay (i) monitors electron transfer from a nearby tryptophan to the flavin and occurs with a time constant of τ(ET) = 0.4 ps. The second decay (ii) is analyzed by spectral decomposition and occurs with a characteristic time constant τ(1) = 31 ps. We reason that hole transport through a tryptophan triad to the protein surface and partial deprotonation of tryptophan cation radical hide behind τ(1). These processes are probably governed by vibrational cooling. Spectral decomposition is used together with anisotropy to obtain the relative orientation of flavin and the final electron donor. This narrows the number of possible electron donors down to two tryptophans. Structural analysis suggests that a set of histidines surrounding the terminal tryptophan may act as proton acceptor and thereby stabilize the radical pair on a 100 ps time scale.

Barrierless photoisomerisation of the "simplest cyanine": joining computational and femtosecond optical spectroscopies to trace the full reaction path.

The photoisomerisation of 1,1'-diethyl-2,2'-pyridocyanine, regarded by Brooker as the simplest cyanine, is examined in methanol by time-resolved experiments and PCM/TD-CAM-B3LYP calculations. Femtosecond transient absorption, fluorescence upconversion, and stimulated Raman scattering, all with broadband coverage, provide a panoramic view of the photoreaction. On the computational side, evolving distributions on an S(1) minimum-energy path are obtained by solving the Smoluchowski equation for drift and diffusion of torsional motion. Absorption and fluorescence bandshapes are calculated and compared to the observations; near-quantitative agreement implies that the entire S(1) path has been observed. Most importantly the global S(1) minimum, i.e. the perpendicular "phantom state" P*, can be identified and characterized in this way. Internal conversion of P* (3.7 ps), assisted by solvent equilibration, leads to the hot ground state. Within 5 ps, vibrational bands of cis and trans isomers are recognized with the help of calculated Raman spectra. The differences between observed and simulated spectra are discussed.

Photoinduced processes in riboflavin: superposition of pi pi*-n pi* states by vibronic coupling, transfer of vibrational coherence, and population dynamics under solvent control.

Femtosecond dynamics of riboflavin, the parent chromophore of biological blue-light receptors, was measured by broadband transient absorption and stationary optical spectroscopy in polar solution. Rich photochemistry is behind the small spectral changes observed: (i) loss of oscillator strength around time zero, (ii) sub-picosecond (ps) spectral relaxation of stimulated emission (SE), and (iii) coherent vibrational motion along a' (in-) and a'' (out-of-plane) modes. Loss of oscillator strength is deduced from the differences in the time-zero spectra obtained in water and DMSO, with stationary spectroscopy and fluorescence decay measurements providing additional support. The spectral difference develops faster than the time resolution (20 fs) and is explained by formation of a superposition state between the optically active (1pi pi*) S1 and closely lying dark (1n pi*) states via vibronic coupling. Subsequent spectral relaxation involves decay of weak SE in the blue, 490 nm, together with rise and red shift of SE at 550 nm. The process is controlled by solvation (characteristic times 0.6 and 0.8 ps in water and DMSO, respectively). Coherent oscillations for a' and a'' modes show up in different regions of the SE band. a'' modes emerge in the blue edge of the SE and dephase faster than solvation. In turn, a' oscillations are found in the SE maximum and dephase on the solvation timescale. The spectral distribution of coherent oscillations according to mode symmetry is used to assign the blue edge of the SE band to a 1n pi*-like state (A''), whereas the optically active 1pi pi* (A') state emits around the SE maximum. The following model comes out: optical excitation occurs to the Franck-Condon pi pi* state, a pi pi*-n pi* superposition state is formed on an ultrafast timescale, vibrational coherence is transferred from a' to a'' modes by pi pi*-n pi* vibronic coupling, and subsequent solvation dynamics alters the pi pi*/n pi* population ratio.

Label-Free Single-Molecule Imaging with Numerical-Aperture-Shaped Interferometric Scattering Microscopy.

Our ability to optically interrogate nanoscopic objects is controlled by the difference between their extinction cross sections and the diffraction-limited area to which light can be confined in the far field. We show that a partially transmissive spatial mask placed near the back focal plane of a high numerical aperture microscope objective enhances the extinction contrast of a scatterer near an interface by approximately T-1/2, where T is the transmissivity of the mask. Numerical-aperture-based differentiation of background from scattered light represents a general approach to increasing extinction contrast and enables routine label-free imaging down to the single-molecule level.

Shaped and Feedback-Controlled Excitation of Single Molecules in the Weak-Field Limit.

Coherent control uses tailored femtosecond pulse shapes to influence quantum pathways and drive a light-induced process toward a specific outcome. There has been a long-standing debate whether the absorption properties or the probability for population to remain in an excited state of a molecule can be influenced by the pulse shape, even if only a single photon is absorbed. Most such experiments are performed on many molecules simultaneously, so that ensemble averaging reduces the access to quantum effects. Here, we demonstrate systematic coherent control experiments on the fluorescence intensity of a single molecule in the weak-field limit. We demonstrate that a delay scan of interfering pulses reproduces the excitation spectrum of the molecule upon Fourier transformation, but that the spectral phase of a pulse sequence does not affect the transition probability. We generalize this result to arbitrary pulse shapes by performing the first closed-loop coherent control experiments on a single molecule.

Fluorescence following excited-state protonation of riboflavin at N(5).

Excited-state protonation of riboflavin in the oxidized form is studied in water. In the -1 < pH < 2 range, neutral and N(1)-protonated riboflavin coexist in the electronic ground state. Transient absorption shows that the protonated form converts to the ground state in <40 fs after optical excitation. Broadband fluorescence upconversion is therefore used to monitor solvation and protonation of the neutral species in the excited singlet state exclusively. A weak fluorescence band around 660 nm is assigned to the product of protonation at N(5). Its radiative rate and quantum yield relative to neutral riboflavin are estimated. Protonation rates agree with proton diffusion times for H(+) concentrations below 5 M but increase at higher acidities, where the average proton distance is below the diameter of the riboflavin molecule.