Coherent control of bond breaking in amino acid complexes with tailored femtosecond pulses.

Intense femtosecond laser pulses, judiciously tailored in an adaptive, optimal control feedback loop were used to break preferentially the acyl-N ("peptide") bond of Ac-Phe-NHMe that may be regarded as a dipeptide model. We show that coherent excitation of complex wave packets in the strong-field regime allows to cleave strong backbone bonds in the molecular system preferentially, while keeping other more labile bonds intact. These results show the potential of pulse shaping as a powerful complementary analytical tool for protein sequencing of large biopolymers in addition to the well-known mass spectrometry and chemical analysis.

High-power fifth-harmonic generation of femtosecond pulses in the vacuum ultraviolet using a Ti:sapphire laser.

We demonstrate the generation of fifth-harmonic pulses at 161 nm, with an energy of up to 600 nJ and 160 fs pulse duration from a Ti:sapphire laser at 1 kHz repetition rate by four-wave difference-frequency mixing in argon-filled waveguides. The efficiency is greatly improved by coupling to higher-order transverse modes, as well as by coating the inner surface of the waveguide. A numerical model of the process yields an understanding of the main effects influencing the harmonic generation.

Electronic coupling in the excited electronic state of stacked DNA base homodimers.

The nature of the electronic coupling of stacked nucleic acid bases adenine (A), thymine (T), and cytosine (C), in A-A, T-T, and C-C complexes in their excited states was investigated; a different character of the electronic coupling for the T-T complex was shown.

Ultrafast processes in OClO molecules excited by femtosecond laser pulses at 386-409 nm.

Ultrafast dissociation dynamics in OClO molecules is studied, induced by femtosecond laser pulses in the wavelength region from 386 to 409 nm, i.e., within the wide absorption band to the (approximately)A (2)A(2) electronic state.

Focusing of scanning light beams below the diffraction limit without near-field spatial control using a saturable absorber and a negative-refraction material.

We show that a scanning light beam can be focused below the diffraction limit without the control of moving near-field elements using the combination of two main components: a light-controlled saturable absorber, which creates seed evanescent components from the beam, and a layer of negative-refraction material, which amplifies the evanescent waves. Focusing to spots with a FWHM in the range of 0.2-0.

Fano line shapes reconsidered: symmetric photoionization peaks from pure continuum excitation.

In a photoionization spectrum in which there is no excitation of the discrete states, but only the underlying continuum, we have observed resonances which appear as symmetric peaks, not the commonly expected window resonances. Furthermore, since the excitation to the unperturbed continuum vanishes, the cross section expected from Fano's configuration interaction theory is identically zero. This shortcoming is removed by the explicit introduction of the phase shifted continuum, which demonstrates that the shape of a resonance, by itself, provides no information about the relative excitation amplitudes to the discrete state and the continuum.

Compression of single-cycle mid-infrared pulses by Raman-active molecular modulators.

We show theoretically how high-order stimulated Raman scattering in the impulsive pump-probe regime can be used for generation of single mid-infrared (MIR) single-cycle pulses. The propagation of MIR probe pulses in a hollow waveguide filled with a Raman-excited gaseous medium, with a probe delay in the maximum of the molecular oscillations, results in spectral broadening covering almost 2 octaves. The spectral phases of this broadening can be compensated for by use of an output glass window with anomalous dispersion in the MIR.

Experimental evidence for supercontinuum generation by fission of higher-order solitons in photonic fibers.

We report on an experimental study of supercontinuum generation in photonic crystal fibers with low-intensity femtosecond pulses, which provides evidence for a novel spectral broadening mechanism. The observed results agree with our theoretical calculations carried out without making the slowly varying envelope approximation. Peculiarities of the measured spectra and their theoretical explanation demonstrate that the reason for the white-light generation in photonic crystal fibers is fission of higher-order solitons into redshifted fundamental solitons and blueshifted nonsolitonic radiation.

Low-temperature-GaAs device used simultaneously as a mode-locking device and as a photoconductive switch.

We present a low-temperature-grown GaAs device that combines the features of mode locking and photoconductive switching. The mode-locking mechanism is based on intensity-dependent defocusing. Additionally, the generated carriers produce an electrical signal in the biased switch geometry.

Supercontinuum generation of higher-order solitons by fission in photonic crystal fibers.

The nonlinear pulse propagation in photonic crystal fibers without slowly varying envelope approximation is studied using an improved variant of first-order wave equation. Supercontinuum generation is shown to be caused by a novel mechanism of spectral broadening through fission of higher-order solitons into redshifted fundamental solitons and blueshifted nonsolitonic radiation. Good agreement with experimental observations is found, and subcycle pulse compression is studied.

Subpicosecond conformational dynamics of small peptides probed by two-dimensional vibrational spectroscopy.

The observation of subpicosecond fluctuations in the conformation of a small peptide in water is demonstrated. We use an experimental method that is specifically sensitive to conformational dynamics taking place on an ultrafast time scale. Complementary molecular-dynamics simulations confirm that the conformational fluctuations exhibit a subpicosecond component, the time scale and amplitude of which agree well with those derived from the experiment.

Collective multielectron tunneling ionization in strong fields.

We investigate the quantum mechanical process of two-electron tunneling in strong external electric fields. Numerical solution of a two-electron s-wave model reveals the existence of collective tunneling ionization in a mode where both electrons stay at equal distance from the nucleus. Otherwise the lagging electron is immediately recaptured.

Phase relations, quasicontinuous spectra and subfemtosecond pulses in high-order stimulated raman scattering with short-pulse excitation.

High-order stimulated Raman scattering for pumping by ps and sub-ps pulses is studied in the frame of a time-domain approach without the slowly varying envelope approximation. Formation of pulse trains with sub-fs durations in the ps-pump regime is demonstrated using external phase compensation. For sub-ps excitation a novel broadening mechanism of Raman lines is predicted that leads to a quasicontinuous spectrum and permits one to generate single sub-fs pulses.

Femtosecond two-photon excited fluorescence of melanin.

Fluorescence of synthetic melanin in dimethyl sulfoxide has been excited by two-photon absorption at 800 nm, using 120 fs pulses with photon flux densities > or = 10(27) cm-2 s-1. The shortest main component of the three-exponential decay of fluorescence is 200 +/- 2 ps. The overall spectral shape is red-shifted with respect to the 400 nm excited fluorescence.