Florian Langhojer

Inherently phase-stable coherent two-dimensional spectroscopy using only conventional optics

We introduce an inherently phase-stable setup for coherent two-dimensional femtosecond spectroscopy in noncollinear box geometry using only conventional beam splitters, mirrors, and delay stages. Avoiding diffractive optics, pulse shapers, and active phase-locking loops, our spectroscopy setup is simple, robust, and works for ultrabroad bandwidths in all spectral regimes (infrared, visible, and ultraviolet).

Coherent two-dimensional ultraviolet spectroscopy in fully noncollinear geometry

We introduce fully noncollinear coherent two-dimensional (2D) spectroscopy in the UV domain with an all-reflective and miniaturized setup design. Phase stability is achieved via pairwise beam manipulation, and the concept can be transferred to all wavelength regimes. Here we present results from an implementation that has been optimized for wavelengths between 250 and 375 nm. Interferometric measurements prove phase stability over several hours. We obtained 2D spectra of the nonpolar UV chromophore p-terphenyl in ethanol, excited with 50 fs pulses at 287 nm.

Ultrafast Photoconversion of the Green Fluorescent Protein Studied by Accumulative Femtosecond Spectroscopy

The irreversible photoconversion of T203V green fluorescent protein (GFP) via decarboxylation is studied under femtosecond excitation using an accumulative product detection method that allows us to measure small conversion efficiencies of down to DeltaOD = 10(-7) absorbance change per pulse. Power studies with 800- and 400-nm pulse excitation reveal that excitation to higher states of the neutral form of the GFP chromophore induces photoconversion very efficiently. The singly excited neutral chromophore is a resonant intermediate of the two-step excitation process that leads to efficient photoconversion. We determine the dynamics of this two-step process by separating the excitation step of the neutral chromophore from the further excitation step to the reactive state in a time-resolved two-color experiment. The dynamics show that a further excitation to the very reactive higher excited state is only possible from the initially excited neutral chromophore and not from the fluorescent intermediate state. For applications of GFP in two-photon fluorescence microscopy, the found photochemical behavior implies that the high intensity conditions used in microscopy can lead to photoconversion easily and care has to be taken to avoid unwanted photoconversion.

Generation of polarization-shaped ultraviolet femtosecond pulses

We experimentally demonstrate the generation and characterization of polarization-shaped femtosecond laser pulses in the ultraviolet at a central wavelength of 400 nm. Near-infrared laser pulses are first polarization shaped and then frequency doubled in an interferometrically stable setup that employs two perpendicularly oriented nonlinear crystals. A new pulse shaper design involving volume phase holographic gratings reduces losses and hence leads to an increase in pulse energy.

Quantum control of the photoinduced Wolff rearrangement of diazonaphthoquinone in the condensed phase

A shaped UV pump–MIR probe setup is employed for quantum control of the photoinduced Wolff rearrangement reaction of diazonaphthoquinone (DNQ) dissolved in methanol, yielding a ketene photoproduct. Time-resolved vibrational spectroscopy is a well-suited tool to monitor a photoreaction in the liquid phase as the narrow vibrational lines allow the observation of structural changes. Especially in the mid-infrared region, marker modes originating from different photoproducts can be identified unambiguously providing suitable feedback signals for open-loop or closed-loop control schemes. We report an experiment where the initiation of a complicated structural change of a molecule, involving bond cleavage and rearrangement, in the liquid phase can be controlled and mechanistic insight is obtained. Single-parameter scans show that the molecule is sensitive to intrapulse dumping during the excitation. Adaptive optimizations lead to pulse structures which can be understood consistently with this dumping mechanism.

Polarization-shaped femtosecond laser pulses in the ultraviolet

We present an experimental concept for the generation and characterization of polarization-shaped femtosecond laser pulses in the ultraviolet. Polarization-shaped laser pulses are frequency-doubled in an interferometrically stable setup comprising two perpendicularly oriented nonlinear crystals. Dual-channel spectral interferometry is employed to fully characterize the electric field of the polarization-shaped ultraviolet pulses. The method is experimentally demonstrated for a central wavelength of 400 nm. Advantages and prospective applications, as well as limitations and possible alternatives, are discussed.

Product accumulation for ultrasensitive femtochemistry

We present a novel experimental method for studying photochemical reactions that involve permanent products. The accumulation of photoproducts facilitates the measurement of extremely small product yields. A calibration of the setup accounts for diffusion effects, and the experimental results can be expressed in terms of single-pulse photochemical efficiencies. A demonstration experiment on indocyanine green (ICG) is presented. The general method is suited both for femtosecond spectroscopy and quantum control experiments.

Accumulative quantum control of photochemical reactions

We demonstrate quantum control over photoreactions in liquid phase involving chemical bond breaking. Stable photoproducts from indocyanine green and green fluorescent protein are generated in a novel accumulative scheme with high product detection sensitivity.