Recoil Inversion in the Photodissociation of Carbonyl Sulfide near 234 nm.

We report the observation of recoil inversion of the CO (v=0, J_{CO}=66) state in the UV dissociation of lab-frame oriented carbonyl sulfide (OCS). This state is ejected in the opposite direction with respect to all other (>30) states and in absence of any OCS rotation, thus resulting in spatial filtering of this particular high-J rovibrational state. This inversion is caused by resonances occurring in shallow local minima of the molecular potential, which bring the sulfur closer to the oxygen than the carbon atom, and is a striking example where such subtleties severely modify the photofragment trajectories.

Wavelength dependent photoelectron circular dichroism of limonene studied by femtosecond multiphoton laser ionization and electron-ion coincidence imaging.

Enantiomers of the monoterpene limonene have been investigated by (2 + 1) resonance enhanced multiphoton ionization and photoelectron circular dichroism employing tuneable, circularly polarized femtosecond laser pulses. Electron imaging detection provides 3D momentum measurement while electron-ion coincidence detection can be used to mass-tag individual electrons. Additional filtering, by accepting only parent ion tagged electrons, can be then used to provide discrimination against higher energy dissociative ionization mechanisms where more than three photons are absorbed to better delineate the two photon resonant, one photon ionization pathway.

Enantiomer-specific analysis of multi-component mixtures by correlated electron imaging-ion mass spectrometry.

Simultaneous, enantiomer-specific identification of chiral molecules in multi-component mixtures is extremely challenging. Many established techniques for single-component analysis fail to provide selectivity in multi-component mixtures and lack sensitivity for dilute samples. Here we show how enantiomers may be differentiated by mass-selected photoelectron circular dichroism using an electron-ion coincidence imaging spectrometer.

Enantioselective femtosecond laser photoionization spectrometry of limonene using photoelectron circular dichroism.

Limonene is ionized by circularly polarized 420 nm femtosecond laser pulses. Ion mass and photoelectron energy spectra identify the dominant (2 + 1) multiphoton ionization mechanism, aided by TDDFT calculations of the Rydberg excitations. Photoelectron circular dichroism measurements on pure enantiomers reveal a chiral asymmetry of ±4 %.

Measurement of the density profile of pure and seeded molecular beams by femtosecond ion imaging.

Here, we report on femtosecond ion imaging experiments to measure the density profile of a pulsed supersonic molecular beam. Ion images are measured for both a molecular beam and bulk gas under identical experimental conditions via femtosecond multiphoton ionization of Xe atoms. We report the density profile of the molecular beam, and the measured absolute density is compared with theoretical calculations of the centre line beam density.

Chiral asymmetry in the multiphoton ionization of methyloxirane using femtosecond electron-ion coincidence imaging.

Multiphoton photoelectron circular dichroism (MP-PECD) has been observed as an asymmetry in the angular distribution of photoelectrons emitted in the ionization of pure enantiomers of the small chiral molecule methyloxirane using a femtosecond laser operated at 420 nm. Energetically, this requires the uptake of four photons. By switching the laser between left- and right-circular polarization, and observing the differences in the full three-dimensional electron momentum distribution recorded in an electron-ion coincidence technique, the chiral (odd) terms in the angular distribution expression can be isolated.

Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection.

Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector.

Detecting chirality in molecules by imaging photoelectron circular dichroism.

In this Perspective we discuss photoelectron circular dichroism (PECD), a relatively novel technique that can detect chiral molecules with high sensitivity. PECD has an enantiomeric sensitivity of typically 1-10%, which is two to three orders of magnitude larger than that of the widely employed technique of circular dichroism (CD). In PECD a chiral molecule is photoionized with circular polarized light, and the photoelectron angular scattering distribution is detected using particle imaging techniques.

Velocity map photoelectron-photoion coincidence imaging on a single detector.

Here we report on a new simplified setup for velocity map photoelectron-photoion coincidence imaging using only a single particle detector. We show that both photoelectrons and photoions can be extracted toward the same micro-channel-plate delay line detector by fast switching of the high voltages on the ion optics. This single detector setup retains essentially all the features of a standard two-detector coincidence imaging setup, viz.

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.

Towards the complete experiment: measurement of S((1)D2) polarization in correlation with single rotational states of CO(J) from the photodissociation of oriented OCS(v2 = 1|JlM = 111).

In this paper we report slice imaging polarization experiments on the state-to-state photodissociation at 42,594 cm(-1) of spatially oriented OCS(v(2) = 1|JlM = 111) → CO(J) + S((1)D(2)). Slice images were measured of the three-dimensional recoil distribution of the S((1)D(2)) photofragment for different polarization geometries of the photolysis and probe laser. The high resolution slice images show well separated velocity rings in the S((1)D(2)) velocity distribution.

Photoelectron photoion coincidence imaging of ultrafast control in multichannel molecular dynamics.

The control of multichannel ionic fragmentation dynamics in CF3I is studied by femtosecond pulse shaping and velocity map photoelectron photoion coincidence imaging. When CF3I is photoexcited with femtosecond laser pulses around 540 nm there are two major ions observed in the time-of-flight mass spectrum, the parent CF3I+ ion and the CF3+ fragment ion. In this first study we focussed on the influence of LCD-shaped laser pulses on the molecular dynamics.

Toward elucidating the mechanism of femtosecond pulse shaping control in photodynamics of molecules by velocity map photoelectron and ion imaging.

The control of photofragmentation and ionization in a polyatomic molecule has been studied by femtosecond chirped laser pulse excitation and velocity map photoelectron and ion imaging. The experiments aimed at controlling and investigating the photodynamics in CH(2)BrCl using tunable chirped femtosecond pulses in the visible wavelength region 509-540 nm at maximum intensities of about 4x10(13) W/cm(2). We observe that the time-of-flight mass spectra as well as the photoelectron images can be strongly modified by manipulating the chirp parameter of ultrashort laser pulses.

A short pulse (7 micros FWHM) and high repetition rate (dc-5 kHz) cantilever piezovalve for pulsed atomic and molecular beams.

In this paper we report on the design and operation of a novel piezovalve for the production of short pulsed atomic or molecular beams. The high speed valve operates on the principle of a cantilever piezo. The only moving part, besides the cantilever piezo itself, is a very small O-ring that forms the vacuum seal.

Coherent oscillatory femtosecond dynamics in multichannel photodynamics of NO2 studied by spatially masked electron imaging.

The femtosecond multiphoton photoionization and dissociation dynamics of NO(2) have been studied in a two-color pump-probe experiment at 400 and 266 nm using velocity map ion imaging in conjunction with photoelectron imaging. We report here a series of experiments focusing on the oscillatory patterns in pump-probe transients of the photoelectron signal. By using the technique of spatially masked imaging detection, we can select different photoelectron channels enabling the rapid measurement of energy selected transients with good signal-to-noise ratio.

In situ characterization of a cold and short pulsed molecular beam by femtosecond ion imaging.

In this paper we report on the in situ characterization of the cold velocity distribution of a pulsed molecular beam produced by a novel cantilever piezo valve. The velocity distribution is measured at various temporal positions within the pulsed expansion using femtosecond velocity map ion imaging. It is shown that the universal detection of molecules by multi-photon femtosecond velocity map ion imaging can provide directly the velocity distribution with excellent velocity resolution.

Imaging the rotationally state-selected NO(A,n) product from the predissociation of the A state of the NO-Ar van der Waals cluster.

The origin of the resonant structures in the spectrum of the predissociative part of the A state in the NO-Ar van der Waals cluster has been investigated. We have employed direct excitation to the predissociative part of the NO-Ar A state followed by rotational state selective ionization of the NO fragment. Velocity map imaging of the NO ion yields the recoil energy of the rotational state-selected fragment.

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.

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.

High-resolution slice imaging of quantum state-to-state photodissociation of methyl bromide.

The photodissociation of rotationally state-selected methyl bromide is studied in the wavelength region between 213 and 235 nm using slice imaging. A hexapole state selector is used to focus a single (JK=11) rotational quantum state of the parent molecule, and a high speed slice imaging detector measures directly the three-dimensional recoil distribution of the methyl fragment. Experiments were performed on both normal (CH(3)Br) and deuterated (CD(3)Br) parent molecules.

Slice imaging of the quantum state-to-state cross section for photodissociation of state-selected rovibrational bending states of OCS (v2=0,1,2/JlM)+hnu-->CO(J)+S(1D2).

Using hexapole quantum state-selection of OCS (v(2)=0,1,2/JlM) and high-resolution slice imaging of quantum state-selected CO(J), the state-to-state cross section OCS (v(2)=0,1,2/JlM)+hnu-->CO(J)+S((1)D(2)) was measured for bending states up to v(2)=2. The population density of the state-selected OCS (v(2)=0,1,2 /JlM) in the molecular beam was obtained by resonantly enhanced multiphoton ionization of OCS and comparison with room temperature bulk gas. A strong increase of the cross section with increasing bending state is observed for CO(J) in the high J region, J=60-67.

Slice imaging of quantum state-to-state photodissociation dynamics of OCS.

Slice imaging experiments are reported for the quantum state-to-state photodissociation dynamics of OCS. Both one-laser and two-laser experiments are presented detecting CO(J) or S((1)D(2)) photofragments from the dissociation of hexapole state-selected OCS(v(2) = 0,1,2 / J = 1,2) molecules. We present data using our recently developed large frame CCD centroiding detector and have implemented a new high speed MCP high voltage pulser with an effective slice width of only 6 ns.

High resolution slice imaging of a molecular speed distribution.

High resolution slice imaging experiments are reported measuring the speed distribution of molecular fragments, recoiling at a most probable speed v(mp), with a full-width-half-maximum (FWHM) speed resolution near the permille level: FWHM(v)/v(mp) = 1.9 x 10(-3). We implemented a high resolution single-particle slice imaging detector and used a two-colour resonance-enhanced multi-photon ionisation (REMPI) scheme to reduce broadening of the speed distribution due to the electron kick.

Imaging of ultrafast molecular elimination reactions.

Ultrafast molecular elimination reactions are studied using the velocity map ion imaging technique in combination with femtosecond pump-probe laser excitation. A pump laser is used to initiate the dissociative reaction, and after a predetermined time delay a probe laser "interrogates" the molecular system. Ionic fragments are detected with a two-dimensional velocity map imaging detector providing detailed information about the energetic and vectorial properties of mass selected photofragments.

State-to-state photodissociation of carbonyl sulfide (nu2=0,1/JlM). II. The effect of initial bending on coherence of S(1D2) polarization.

Photodissociation studies using ion imaging are reported, measuring the coherence of the polarization of the S((1)D(2)) fragment from the photolysis of single-quantum state-selected carbonyl sulfide (OCS) at 223 and 230 nm. A hexapole state-selector focuses a molecular beam of OCS parent molecules in the ground state (nu2=0mid R:JM=10) or in the first excited bending state (nu2=1mid R:JlM=111). At 230 nm photolysis the Im[a1 (1)(parallel, perpendicular)] moment for the fast S(1D2) channel increases by about 50% when the initial OCS parent state changes from the vibrationless ground state to the first excited bending state.