Marcel Drabbels

A Study of the Singlet-Triplet Perturbations in the a 1au State of Acetylene by High-Resolution Ultraviolet Spectroscopy

Laser‐induced fluorescence spectra of the 330 K10 and 340 K10 vibronic bands of the A 1Au←X 1Σ+g transition in acetylene have been recorded with a resolution of 18 MHz. Each rotational transition consists of a group of lines due to coupling of the electronically excited singlet state with isoenergetic triplet states. Using the standard deconvolution procedure the singlet–triplet coupling elements and the density of coupled triplet states are derived for rotational levels up to J=4 in both bands. From the density of coupled triplet states it is concluded that the A 1Au state is perturbed by the T1 3B2 state. Magnetic field measurements have shown that the predissociation of acetylene in the 4ν3’ vibrational level of the A state is caused by a coupling via the T1 3B2 state with predissociating vibrational levels of the electronic ground state.

A far infrared laser sideband spectrometer in the frequency region 550–2700 GHz

This paper describes a tunable far‐infrared (FIR) spectrometer. Tunable radiation is obtained by frequency mixing, fixed frequency FIR laser radiation and tunable microwave radiation in Schottky barrier diodes. An optically pumped laser and an HCN discharge laser are used as FIR sources and klystrons in the frequency range of 22–114 GHz as microwave sources. This yields an 85% coverage of the frequency region between 550 and 2700 GHz. Up to sixth order sidebands have been generated and used for spectroscopy. The ultimate sensitivity corresponds to a minimum detectable fractional absorption of 10−5 at 1‐s RC time. The applicability of the spectrometer in high‐resolution spectroscopy of transient species has been demonstrated by the observation of spectra of OD and N2H+. New laser emissions of optically pumped CH2F2 have been found and accurate frequencies have been determined for some of them.

Acetone, a laser-induced fluorescence study with rotational resolution at 320 nm

The forbidden S1 <-- S0 transition of acetone has been investigated by laser-induced fluorescence measurements with a resolution of 270 MHz. The rotational structure demonstrates, that (i) one deals with a-type transitions and (ii) there is a strong coupling between the torsional motion of the two CH3 groups and the tunneling, out-of-plane wagging motion (nu(23)) of acetone. The interpretation of torsion-vibrational combination bands is less conclusive and thus the discussion still has a preliminary character.

The correlated product state distribution of ketene photodissociation at 308 nm

The correlated product state distribution for ketene photodissociation (CH2CO-->CH2+CO) at 308 nm has been measured by using quantum-state-specific metastable time-of-flight (TOF) spectroscopy. This distribution is a matrix whose elements are the probability that if CO is produced in the dissociation with quantum-state \n(CO)], CH2 will be produced with quantum-state \n(CH2)]. It was found that ketene photodissociation yields CH2 in three resolved states; the (1)A(1) 1(000), and (1)A(1)(010) states of CH2 are the major channels, while the B-3(1) State is a minor channel. In addition to this scalar distribution, the vector correlations between the recoil velocity and the angular momentum of the CO fragment (v . j correlation), expressed by the beta(0)(0)(22) bipolar moment, have also been obtained as a function of the kinetic energy release of the photoreaction. The correlated product state distribution was found not to follow the predictions of phase space theory, suggesting that dynamic hindrances exist in the photoreaction that have not been previously observed. A phase space theory calculation with restricted impact parameter values was also performed and compared to experiment. The impact parameter restricted phase space theory more accurately reproduced all of the correlated product state information obtained in this work as well as previous uncorrelated product state distributions for CH2 and CO. Both the ranges and the values of the allowed impact parameters obtained from these restricted calculations increase as the rotational energy of CO increases. Also, the values of the allowed impact parameters for (1)A(1)(010) CH2 are larger than for (1)A(1)(000) CH2. This strongly suggests that C-C-O bending modes are hindered at the transition state and therefore play an important role in the photodissociation.

Photodissociation of alkyl iodides in helium nanodroplets. I. Kinetic energy transfer

The photodissociation of (fluorinated) alkyl iodides in helium nanodroplets at a wavelength of 266 nm has been investigated by means of ion imaging techniques. It is found that a significant fraction of the created fragments escapes from the helium droplets. The speed and kinetic energy distributions of these fragments are found to be notably modified with respect to the corresponding gas phase distributions. The fragments, furthermore, show a speed dependent angular distribution. The loss of kinetic energy as well as the reduction of the anisotropy parameter show a strong mass dependence. These observations point to a nonthermal escape process in which the kinetic energy and momentum transfer from the fragments to the solvent is governed by binary collisions with the individual helium atoms making up the droplet. Monte Carlo simulations based on hard-sphere binary collisions substantiate this interpretation of the data.

IR Spectroscopy of Molecular Ions by Nonthermal Ion Ejection from Helium Nanodroplets

Infrared spectroscopy provides a means to determine the intrinsic geometrical structures of molecules. Here we present a novel spectroscopic method that uses superfluid helium nanodroplets to record IR spectra of cold molecular ions, in this particular case aniline cations. The method is based on the detection of ions that are ejected from the helium droplets following vibrational excitation of these ions. We find that spectra can be recorded with a high sensitivity and that they exhibit only a small matrix shift. The widths of the individual transitions depend on the excited vibrational level and are thought to be related to the interaction of the ion with the surrounding helium solvent shells.

A modular end-station for atomic, molecular, and cluster science at the low density matter beamline of FERMI@Elettra

The low density matter end-station at the new seeded free electron laser FERMI@Elettra is a versatile instrument for the study of atoms, molecules and clusters by means of electron and ion spectroscopies. Beams of atoms, molecules and helium droplets as well as clusters of atoms, molecules and metals can be produced by three different pulsed valves. The atomic and molecular beams may be seeded, and the clusters and droplets may be pure, or doped with other atoms and molecules. The electrons and ions produced by the ionization and fragmentation of the samples by the intense light of FERMI can be analysed by the available spectrometers, to give mass spectra and energy as well as angular distributions of charged particles. The design of the detector allows simultaneous detection of electrons and ions using velocity map imaging and time-of-flight techniques respectively. The instruments have a high energy/mass resolution and large solid-angle collection efficiency. We describe the current status of the apparatus and illustrate the potential for future experiments.

Spectroscopy on Rydberg states of sodium atoms on the surface of helium nanodroplets

One- and two-photon excitation spectra of sodium atoms on the surface of helium droplets are reported. The spectra are recorded by monitoring the photoionization yield of desorbed atoms as function of excitation frequency. The excitation spectra involving states with principal quantum number up to n = 6 can be reproduced by a pseudodiatomic model where the helium droplet is treated as a single atom. For the lowest excited states of sodium, the effective interaction potentials for this system can be approximated by the sum of NaHe pair potentials. For the higher excited states, the interaction of the sodium valence electron with the helium induces significant configuration mixing, leading to a failure of this approach. For these states, effective interaction potentials based on a perturbative treatment of the interactions between the valence electron, the alkali positive core, and the helium, as described in detail in the accompanying publication, yield excellent agreement with experiment.

Determination of electric dipole moments and transition probabilities of low‐lying singlet states of CO

Transitions from the X 1Σ+(v=0) ground state of the carbon monoxide molecule to the electronically excited A 1Π(v=0), B 1Σ+(v=0), and C 1Σ+(v=0) states have been studied by 2‐photon laser induced fluorescence spectroscopy. Accurate molecular constants for the B and C state have been determined. The electric dipole moments for all three electronically excited states have been deduced from the observed Stark effects. The dipole moments for the A, B, and C states are found to be 0.335±0.013, 1.95±0.03, and 4.50±0.07 D, respectively. From the observed radiative lifetimes the transition probabilities of the B–A, B–X and C–B, C–A, and C–X transitions have been determined.

Mid-infrared spectroscopy of molecular ions in helium nanodroplets.

High resolution IR spectra of aniline, styrene, and 1,1-diphenylethylene cations embedded in superfluid helium nanodroplets have been recorded in the 300-1700 cm(-1) range using a free-electron laser as radiation source. Comparison of the spectra with available gas phase data reveals that the helium environment induces no significant matrix shift nor leads to an observable line broadening of the resonances. In addition, the IR spectra have provided new and improved vibrational transition frequencies for the cations investigated, as well as for neutral aniline and styrene. Indications have been found that the ions desolvate from the droplets after excitation by a non-evaporative process in which they are ejected from the helium droplets. The kinetic energy of the ejected ions is found to be ion specific and to depend only weakly on the excitation energy.