Highly stable, 15 W, few-cycle, 65 mrad CEP-noise mid-IR OPCPA for statistical physics.

We demonstrate a 100 kHz optical parametric chirped-pulse amplifier delivering under 4-cycle (38 fs) pulses at ~3.2 µm with an average power of 15.2 W with a pulse-to-pulse energy stability <0.7% rms and a single-shot CEP noise of 65 mrad RMS over 8h. This source is continuously monitored, by using a fast 100 kHz data acquisition device, and presents an extreme stability, in the short and long terms.

4-W, 100-kHz, few-cycle mid-infrared source with sub-100-mrad carrier-envelope phase noise.

We demonstrate an optical parametric chirped-pulse amplifier delivering 4-cycles (38-fs) pulses centered around 3.1 µm at 100-kHz repetition rate with an average power of 4 W and an undersampled single-shot carrier-envelope phase noise of 81 mrad recorded over 25 min. The amplifier is pumped by a ~1.1 ps, Yb-YAG, thin-disk regenerative amplifier and seeded with a supercontinuum generated in bulk YAG from the same pump pulses. Carrier-envelope phase stability is passively achieved through difference-frequency generation between pump and seed pulses. An additional active stabilization at 10 kHz combining 2f-to-f interferometry and a LiNbO3 acousto-optic programmable dispersive filter achieves a record low phase noise.

Direct mid-infrared femtosecond pulse shaping with a calomel acousto-optic programmable dispersive filter.

Direct amplitude and phase shaping of mid-infrared femtosecond pulses is realized with a calomel-based acousto-optic programmable dispersive filter transparent between 0.4 and 20 µm. The shaped pulse electric field is fully characterized with high accuracy, using chirped-pulse upconversion and time-encoded arrangement spectral phase interferometry for direct electric field reconstruction techniques. Complex mid-infrared pulse shapes at a center wavelength of 4.9 µm are generated with a spectral resolution of 14 cm(-1), which exceeds by a factor of 5 the reported experimental resolutions of calomel-based filters.

Bessel beam transformation by anisotropic crystals.

Transformation of Bessel beams by biaxial and uniaxial crystals is investigated experimentally and theoretically. Experimental observations show beam symmetry changing and formation of complex intensity patterns, depending on the orientation of the crystal. These patterns can appear as a regular system of peak intensities. Results of numerical calculations support the experimental findings.

Ultrafast dynamics of isolated phenylcarbenes followed by femtosecond time-resolved velocity map imaging.

The ultrafast dynamics of two carbene model systems, chlorophenylcarbene (CPC) and trifluoromethylphenylcarbene (TFPC), has been studied in a molecular beam. Velocity map imaging aids optimizing the pyrolysis conditions for a clean generation of reactive intermediates by supersonic jet flash pyrolysis. The dynamics was followed in real time by time-resolved mass spectroscopy and photoion and photoelectron imaging. CPC was excited at 265 nm into the 3 (1)A' state, corresponding to excitation from a pi-orbital of the aromatic ring into the lowest unoccupied molecular orbital, which contains the p-orbital at the carbene center. The experimental results suggest a three step deactivation process in agreement with computations. TFPC exhibits two absorption bands in the 36,000 cm(-1) and 41,000 cm(-1) range and gives rise to very similar dynamics, although it has a triplet ground state. The experimental data were augmented by computations.

Femtosecond dynamics of isolated phenylcarbenes.

Understanding the primary photophysical processes in molecules is essential for interpreting their photochemistry, because molecules rarely react from the initially excited electronic state. In this study the ultrafast excited-state dynamics of chlorophenylcarbene (CPC) and trifluoromethylphenylcarbene (TFPC), two species that are considered as models for carbene dynamics, were investigated by femtosecond time-resolved pump probe spectroscopy in the gas phase. Their dynamics was followed in real time by time-resolved photoionization and photoelectron imaging. CPC was excited at 265 nm into the 3 1A' state, corresponding to excitation from a pi-orbital of the aromatic ring into the LUMO. The LUMO contains a contribution of the p-orbital at the carbene center. Three time constants are apparent in the photoelectron images: A fast decay process with tau1 approximately 40 fs, a second time constant of tau2 approximatley 350 fs, and an additional time constant of tau3 approximately 1 ps. The third time constant is only visible in the time-dependence of low kinetic energy electrons. Due to the dense manifold of excited states between 3.9 and 5 eV, known from ab initio calculations, the recorded time-resolved electron images show broad and unstructured bands. A clear population transfer between the states thus can not directly be observed. The fast deactivation process is linked to either a population transfer between the strongly coupled excited states between 3.9 and 5.0 eV or the movement of the produced wave packet out of the Franck-Condon region. Since the third long time constant is only visible for photoelectrons at low kinetic energy, evidence is given that this time constant corresponds to the lifetime of the lowest excited A 1A' state. The remaining time constant reflects a deactivation of the manifold of states in the range 3.9-5.0 eV down to the A 1A' state.

Femtosecond dynamics of the tert-butyl radical, t-C4H9.

The excited-state dynamics of the tert-butyl radical, t-C4H9, was investigated by femtosecond time-resolved photoionization and photoelectron spectroscopy. The experiments were supported by ab initio calculations. tert-Butyl radicals, generated by flash pyrolysis of azo-tert-butane, were excited into the A 2A1 (3s) state between 347 and 307 nm and the 3p band at 274 and 268 nm and ionized by 810-nm radiation, in a [1 + 2'] or [1 + 3'] process. Electronic structure calculations confirm that the two states are of s and p Rydberg characters, respectively. The carbon framework becomes planar and thus ion-like in both states. The photoelectron spectra are broad and seem to be mediated by accidental intermediate resonances in the probe step. All time-resolved photoelectron spectra can be described by a single decay time. For the A 2A1 state, lifetimes between 180 and 69 fs were measured. Surprisingly, a much longer lifetime of around 2 ps was found for the 3p state. To understand the decay dynamics, the potential energy was computed as a function of several important nuclear coordinates. A [1,2] H-atom shift to the isobutyl radical seems not to be important for the excited-state dynamics. Qualitative considerations indicate curve crossings between the ground state, the 3s state, and a valence state along the asymmetric C-C stretch coordinate that correlates to the dimethylcarbene + methyl product channel. The implications of the present study for earlier work on the nanosecond time scale are discussed.

Photodissociation of thymine.

We discuss the photochemistry and photodissociation dynamics of thymine as revealed by two-colour photofragment Doppler spectroscopy and by one-colour slice imaging. Thymine is optically excited into the pipi* state, known to deactivate quickly. The H atom photofragment spectra are dominated by two-photon excitation processes with subsequent statistical dissociation. This can be explained by absorption of a second photon from a long-lived dark state to a highly excited state that quickly deactivates to the electronic ground state. No evidence was found for an important role of the pisigma* excited state identified in adenine and many other heterocyclic molecules.

The excited-state dynamics of phycocyanobilin in dependence on the excitation wavelength.

The primary light-induced processes of phycocyanobilin were studied by means of transient-grating spectroscopy, whereby the excitation wavelength was varied over the spectral region of the ground-state absorption. On the basis of the results obtained, both the rate of the photoreaction in phycocyanobilin and the ratio of the decay of different excited-state species via two decay channels depend on the excitation wavelength. Furthermore, the formation of the photoreaction product is also dependent on the pump color. These data support a recently established model for the primary photoprocesses in phycocyanobilin. In addition, phycocyanobilin protonated at the basic pyrrolenine-type nitrogen atom was included in the transient absorption study. The decay behavior was found to be almost unchanged when compared with the unprotonated form, and this suggests that protonation of the tetrapyrrole ring structure has no effect on the overall photochemistry.