Predicting intense-field photoionization of atoms and molecules from their linear photoabsorption spectra in the ionization continuum

We report a new approach to intense-field photoionization that is based on the ad hoc assumption that m photons of energy arriving within a typical electronic response time are effectively equivalent to a single photon of energy . The heuristic model contains no adjustable parameters and unifies apparent multiphoton and field aspects. Moreover, nonsequential, suppressed and above-threshold ionization phenomena become readily understandable. Predicted ionization intensities are in satisfactory agreement with available experimental data ranging from C₆H₆ to Ne^{3 +} , from femtosecond to nanosecond laser pulses, and from ultraviolet to infrared laser radiation.Received: 20 January 2004, Published online: 17 August 2004PACS: 32.80.Rm Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states) - 32.80.Wr Other multiphoton processes - 42.50.Hz Strong-field excitation of optical transitions in quantum systems; multiphoton processes; dynamic Stark shift     

Infrared laser specific reactions of boranes. Conversion of diborane to icosaborane(16), B20H16

Monochromatic low power radiation of a CO₂ laser (1.5 W) initiates in diborane B₂H₆ a chain reaction in the course of which icosaborane(16) B₂₀H₁₆ is formed as the main product. This reaction is accompanied by visible luminescence.     

Programmable amplitude- and phase-modulated femtosecond laser pulses in the mid-infrared

We present a scheme to produce programmable phase- and amplitude-modulated femtosecond laser pulses in the mid-infrared regime of 3-10mum by difference frequency mixing. The 80-fs signal output of an optical parametric amplifier is shaped with a liquid-crystal mask and mixed in an AgGaS(2) crystal with a temporally stretched idler pulse. Without changing the mechanical alignment, we produce programmable amplitude modulations and chirped pulses at lambda=3mum with energy as high has thas 1muJ . This scheme, further, allows the generation of controllable pulse sequences. The results are in good agreement with theoretical simulations.     

Ultrafast vibrational spectroscopy and relaxation in polyatomic molecules: Potential for molecular parallel computing

The feasibility of controlled ultrafast pumping in the mid IR and the probe of the subsequent intramolecular dynamics is illustrated for vibrational excitation of the two metal carbonyls W(CO)₆ and Mn(CO)₅Br in solution. Pumping and probing is performed by short, 130 fs, pulses centered at about 2000 cm⁻¹. Frequency resolved measurements of the time delayed probe pulse are performed. Measured two dimensional spectra are fitted by a kinetic scheme that models the vibrational dynamics. Fast relaxation is solvent induced with the solvent acting also as a heat bath. The (several) probe signals in the experiment can be thought of as the response of a finite state logic machine. This suggests that the molecular machine can act as an ultrafast (petaHertz) processor. The number of internal (memory) states of the machine is determined by the number of vibrational states in the kinetic scheme that can fit the observed relaxation. The number of outputs of the machine is the number of the several different available probe signals. It is shown that the machine is massively parallel because in each (sub ps) time step it produces an entire vector as an output and that each component of the output vector is, by itself, a transform over the input. Beyond that, the machine can produce a (finite number of) different output vectors in sequential time steps.     

Chirp-driven vibrational distribution in transition metal carbonyl complexes

In this theoretical study vibrational ladder climbing in transition metal carbonyl complexes, as a possible means to initialize chemical ground state reactions, and the resulting vibrational population distribution using chirped mid-infrared femtosecond laser pulses is investigated. Our model system is MnBr(CO)(5), a strong IR-absorber within an experimentally easily accessible wavelength region. Special emphasis is put on the perturbation due to additional vibrational modes, especially on one, which allows dissociation at low energies. The related potential energy surface for the three representative modes is calculated, whereon quantum dynamics calculations, including the laser-molecule interaction, are performed. No significant coupling could be detected, neither in the bound, nor in the dissociative region. Contrarily, we found a dynamical barrier even for energies high above the dissociation limit. Different vibrational population distributions after the laser excitation of the CO stretching mode could be generated in dependence of the chirp parameters. Based on these findings we simulated the laser excitation corresponding to an experiment by M. Joffre et al., Proc. Natl. Acad. Ssi. U. S. A., 2004, 101(36), 13216-13220, where coherent vibrational ladder climbing in carboxyhemoglobin was demonstrated and we could offer an explanation for an open question, concerning the interpretation of the spectroscopic data.     

Independently controllable multiline emission from a TEA CO2 laser

Spatial separation of wavelengths in a CO₂-laser resonator helps to avoid competitions. We have achieved this by means of a nearly concentric resonator with a grating or prism in its center. Thus, we demonstrated independent multiline emission with a variety of output spectra. The temporal sequence of the lines was conveniently controlled by varying their losses.     

UV laser photochemistry of acetylene at 193 nm

ArF laser photolysis of acetylene at 193 nm yields diacetylene, ethylene and hydrogen (besides a polymer). No benzene or vinylacetylene is formed. Photolysis with deuterium gives no deuterated compounds. These observations are taken as evidence for a pure excited-molecule mechanism based upon C₂H ₂ ^* (¹ A _u).     

Femtosecond pulse shaping in the mid infrared by difference-frequency mixing

The generation of programmable complex femtosecond pulses in the mid infrared (3–10 μm) with high precision is reported. Designed pulse shapes in the near infrared (1–1.6 μm) are transferred to the mid infrared via difference-frequency mixing with a second infrared pulse spectrally narrowed in a zero-dispersion compressor. In particular, pulse sequences with variable relative phases have been obtained. The control of the pulse properties is achieved purely electronically, allowing for implementation into a feedback loop. Received: 12 December 2003 / Published online: 3 April 2003 RID="*" ID="*"Corresponding author. Fax: +49-89/32905-200, E-mail: mcm@mpq.mpg.de     

Absorption of CO2 laser pulses at different wavelengths by ground-state and vibrationally heated SF6

The absorption of CO₂ laser pulses by low pressure SF₆ gas has been investigated over a wide range of energy fluxes. For laser energy fluxes of 0.01–1 J cm^-2 the effective absorption cross section varies between 0.2 and 2 × 10^-18 cm². For each laser line an individual dependence on the energy is found and in some cases minor changes in the absorption behaviour seem to occur around 0.1 J cm^-2. SF₆ excited with an average vibrational energy content of up to 20 photons/molecule does not absorb measurable amounts of 9.4 μm laser light. The influence of various SF₆ and Ar pressures on the temporal shape of the transmitted pulses has been investigated.