Femtosecond 2 + 1 Resonance-Enhanced Multiphoton Ionization Spectroscopy of the C-State in Molecular Oxygen.

Coincidence electron-cation imaging is used to characterize the multiphoton ionization of O2 via the v = 4,5 levels of the 3s(3Πg) Rydberg state. A tunable 100 fs laser beam operating in the 271-263 nm region is found to cause a nonresonant ionization across this wavelength range, with an additional resonant ionization channel only observed when tuned to the 3Πg(v = 5) level. A distinct 3s → p wave character is observed in the photoelectron angular distribution for the v = 5 channel when on resonance.

Experimental and Theoretical Investigation of the 3sp(d) Rydberg States of Fenchone by Polarized Laser Resonance-Enhanced-Multiphoton-Ionization and Fourier Transform VUV Absorption Spectroscopy.

The VUV absorption spectrum of fenchone is re-examined using synchrotron radiation Fourier transform spectrometry, revealing new vibrational structure. Picosecond laser (2+1) resonance enhanced multiphoton ionization (REMPI) spectroscopy complements this, providing an alternative view of the 3spd Rydberg excitation region. These spectra display broadly similar appearance, with minor differences that are largely explained by referring to calculated one- and two-photon electronic excitation cross-sections. Both show good agreement with Franck-Condon simulations of the relevant vibrational structures. Parent ion REMPI ionization yields with both femtosecond and picosecond excitation laser pulses are studied as a function of laser polarization and intensity, the latter providing insight into the relative two-photon excitation and one-photon ionization rates. The experimental circular-linear dichroism observed in the parent ion yields varies strongly between the 3s and 3p Rydberg states, in good overall agreement with the calculated two-photon excitation circular-linear dichroism, while corroborating other evidence that the 3pz sub-state plays no more than a very minor role in the (2+1) REMPI spectrum. Vibrationally resolved photoelectron spectra are recorded with picosecond pulse duration (2+1) REMPI at selected intermediate vibrational excitations. The 3s intermediate state displays a very strong Δv=0 propensity on ionization, but the 3p intermediate evidences more complex vibronic dynamics, and we infer some 3p→3s internal conversion prior to ionization.

Optimization of single-cycle terahertz generation in LiNbO3 for sub-50 femtosecond pump pulses.

We compare different tilted-pulse-front pumping schemes for single-cycle THz generation in LiNbO(3) crystals both theoretically and experimentally in terms of conversion efficiency. The conventional setup with a single lens as an imaging element has been found to be highly inefficient in the case of sub-50 fs pump pulses, mainly due to the resulting chromatic aberrations. These aberrations are avoided in the proposed new setup, which employs two concave mirrors in a Keplerian telescope arrangement as the imaging sequence. This partially compensates spherical aberrations and results in a ca. six times higher conversion efficiency in the case of 35-fs optical pump pulse duration compared to the single-lens setup. A THz field strength of 60 kV/cm was obtained using 0.5 mJ pump pulses. The divergence of the THz beam has been found experimentally to depend on the pump imaging scheme employed.

The reaction microscope: imaging and pulse shaping control in photodynamics.

Herein, we review the current capabilities and potential of advanced single-particle imaging techniques to study photodynamics in isolated molecules. These reaction microscopes are able to measure the full three-dimensional energy and angular distribution of (correlated) particles such as electrons and molecular fragments ejected after photoexcitation of molecules. In particular, we discuss the performance and capabilities of a novel photoelectron-photoion coincidence imaging spectrometer constructed at LaserLaB Amsterdam. This microscope was developed for the study of nonadiabatic effects in ultrafast time-resolved experiments. It is specifically targeted at optimal control studies of photodynamics to foster and advance our understanding of mechanisms in optimal control with shaped ultrafast laser pulses. We review a few recent experimental results illustrating the wealth of detailed information that can be obtained in such imaging experiments about the interplay between (shaped) laser fields, molecular dynamics, ionization processes and competing multichannel pathways. Furthermore, the recently developed photoelectron-circular-dichroism imaging technique to detect enantiomers and to study chirality effects will be discussed, as a further illustration of the potential of modern reaction microscopes in stereochemistry.

A photoelectron-photoion coincidence imaging apparatus for femtosecond time-resolved molecular dynamics with electron time-of-flight resolution of sigma=18 ps and energy resolution Delta E/E=3.5%.

We report on the construction and performance of a novel photoelectron-photoion coincidence machine in our laboratory in Amsterdam to measure the full three-dimensional momentum distribution of correlated electrons and ions in femtosecond time-resolved molecular beam experiments. We implemented sets of open electron and ion lenses to time stretch and velocity map the charged particles. Time switched voltages are operated on the particle lenses to enable optimal electric field strengths for velocity map focusing conditions of electrons and ions separately. The position and time sensitive detectors employ microchannel plates (MCPs) in front of delay line detectors. A special effort was made to obtain the time-of-flight (TOF) of the electrons at high temporal resolution using small pore (5 microm) MCPs and implementing fast timing electronics. We measured the TOF distribution of the electrons under our typical coincidence field strengths with a temporal resolution down to sigma=18 ps. We observed that our electron coincidence detector has a timing resolution better than sigma=16 ps, which is mainly determined by the residual transit time spread of the MCPs. The typical electron energy resolution appears to be nearly laser bandwidth limited with a relative resolution of DeltaE(FWHM)/E=3.5% for electrons with kinetic energy near 2 eV. The mass resolution of the ion detector for ions measured in coincidence with electrons is about Deltam(FWHM)/m=14150. The velocity map focusing of our extended source volume of particles, due to the overlap of the molecular beam with the laser beams, results in a parent ion spot on our detector focused down to sigma=115 microm.

Femtosecond time-resolved photoelectron-photoion coincidence imaging of multiphoton multichannel photodynamics in NO2.

The multiphoton multichannel photodynamics of NO(2) has been studied using femtosecond time-resolved coincidence imaging. A novel photoelectron-photoion coincidence imaging machine was developed at the laboratory in Amsterdam employing velocity map imaging and "slow" charged particle extraction using additional electron and ion optics. The NO(2) photodynamics was studied using a two color pump-probe scheme with femtosecond pulses at 400 and 266 nm. The multiphoton excitation produces both NO(2) (+) parent ions and NO(+) fragment ions. Here we mainly present the time dependent photoelectron images in coincidence with NO(2) (+) or NO(+) and the (NO(+),e) photoelectron versus fragment ion kinetic energy correlations. The coincidence photoelectron spectra and the correlated energy distributions make it possible to assign the different dissociation pathways involved. Nonadiabatic dynamics between the ground state and the A (2)B(2) state after absorption of a 400 nm photon is reflected in the transient photoelectron spectrum of the NO(2) (+) parent ion. Furthermore, Rydberg states are believed to be used as "stepping" states responsible for the rather narrow and well-separated photoelectron spectra in the NO(2) (+) parent ion. Slow statistical and fast direct fragmentation of NO(2) (+) after prompt photoelectron ejection is observed leading to formation of NO(+)+O. Fragmentation from both the ground state and the electronically excited a (3)B(2) and b (3)A(2) states of NO(2) (+) is observed. At short pump probe delay times, the dominant multiphoton pathway for NO(+) formation is a 3x400 nm+1x266 nm excitation. At long delay times (>500 fs) two multiphoton pathways are observed. The dominant pathway is a 1x400 nm+2x266 nm photon excitation giving rise to very slow electrons and ions. A second pathway is a 3x400 nm photon absorption to NO(2) Rydberg states followed by dissociation toward neutral electronically and vibrationally excited NO(A (2)Sigma,v=1) fragments, ionized by one 266 nm photon absorption. As is shown in the present study, even though the pump-probe transients are rather featureless the photoelectron-photoion coincidence images show a complex time varying dynamics in NO(2). We present the potential of our novel coincidence imaging machine to unravel in unprecedented detail the various competing pathways in femtosecond time-resolved multichannel multiphoton dynamics of molecules.