Multiphoton ionization of iodine atoms and CF<Subscript> 3</Subscript>I molecules by XeCl laser radiation

We report about effective ionization of iodine atoms and CF₃I molecules under the action of intense XeCl laser radiation (308 nm). The only ion fragment resulting from the irradiation of the CF₃I molecules is the I⁺ ion. We have studied the influence of the intensity, spectral composition, and polarization of the laser radiation used on the intensity of the ion signal and the shape of its time-of-flight peak. Based on the analysis of the results obtained, we have suggested the mechanism of this effect. The conclusion drawn is that the ionization of the iodine atoms by the ordinary XeCl laser with a nonselective cavity results from a three- (2 + 1)-photon REMPI process. This process is in turn due to the presence of accidental two-photon resonances between various spectral components of the laser radiation and the corresponding intermediate excited states of the iodine atom. The probability of ionization of the atoms from their ground state I(²P_3/2) by the radiation of the ordinary XeCl laser is more than two orders of magnitude higher than the probability of their ionization from the metastable state I^*(²P_1/2). The ionization of the CF₃I molecules by the XeCl laser radiation occurs as a result of a four-photon process involving the preliminary one-photon dissociation of these molecules and the subsequent (2 + 1)-photon REMPI of the resultant neutral iodine atoms.     

Radiative lifetimes of the NaRb C(3)1Σ+ state: experiment and theory

Radiative lifetimes for 2≤v^′≤44 rovibronic C¹Σ⁺ state levels of NaRb and quenching collision cross-sections with Rb atoms have been directly measured in a thermal cell by detecting time resolved laser induced fluorescence after pulsed excitation. Many body multipartitioning theory was applied to calculate C¹Σ⁺-X¹Σ⁺ and C¹Σ⁺-A¹Σ⁺ transition dipole moments. The relevant ab initio matrix elements were converted to the C¹Σ⁺ state radiative lifetimes. The strong spin-orbit A¹Σ⁺∼ b³Π coupling effect on the total C → A transition probabilities and lifetimes of the C¹Σ⁺ state is discussed. The measured radiative lifetimes show a decrease from 61 to 34 ns as the v^′ values increase, the results being in good agreement with calculations. The averaged collisional quenching cross-section value σ=(3±1)×10^-14 cm² was determined for NaRb (C¹Σ⁺) + Rb collisions from the Stern-Volmer plots.     

Kinematically complete final state investigations of molecular photodissociation: two- and three-body decay of laser-prepared H 3 3 s ? 2 A 1 '

We have performed kinematically complete investigations of molecular photodissociation of triatomic hydrogen in a fast beam translational spectrometer recently built in Freiburg. The apparatus allows us to investigate laser-induced dissociation of neutral molecules into two, three, or more neutral products. The fragments are detected in coincidence and their vectorial momenta in the center-of-mass frame are determined. We demonstrate the potential of the method at the fragmentation of the 3 s ² A ₁ ^′ ( N = 1, K = 0) state of triatomic hydrogen. In this state, three-body decay into ground state hydrogen atoms H+H+H, two-body predissociation into H+H ₂ (v , J), and photoemission to the H ₃ ground state surface with subsequent two-body decay are competing channels. In the case of two-body predissociation, we determine the rovibrational population in the H ₂ (v , J) fragment. The vibrational distribution of H ₂ is compared with approximate theoretical predictions. For three-body decay, we measure the six-fold differential photodissociation cross-section. To determine accurate final state distributions, the geometric collection efficiency of the apparatus is calculated by a Monte Carlo simulation, and the raw data are corrected for apparatus efficiency. The final state momentum distribution shows pronounced correlation patterns which are characteristic for the dissociation mechanism. For a three-body decay process with a discrete kinetic energy release we have developed a novel data reduction procedure based on the detection of two fragments. The final state distribution determined by this independent method agrees extremely well with that observed in the triple-coincidence data. In addition, this method allows us to fully explore the phase space of the final state and to determine the branching ratios between the two- and three-body decay processes. Received 29 March 2001     

Time-dependent fragment distributions detected via pump-probe ionisation: a theoretical approach

We show how in molecular predissociation a method combining ultrafast pump-probe techniques with a measurement of the relative recoil velocity can map time-dependent neutral fragment distributions into the ionic continuum. With an appropriate probe pulse exciting a resonant transition (such as (1+1) Resonance Enhanced Multiphoton Ionisation, or excitation of ZEKE states), the temporal evolution of fragment distributions can in principle be measured. Numerical simulations on NaI predissociation are compared to a simple approximate mapping interpretation. The results are discussed in terms of the interplay between temporal and energetic resolution with respect to current experimental limitations. Received 13 October 2000 and Received in final form 8 December 2000     

Isotopomer selective optimization of <Superscript>39</Superscript>K<Superscript>85</Superscript>Rb<Superscript>+</Superscript> and <Superscript>41</Superscript>K<Superscript>87</Superscript>Rb<Superscript>+</Superscript> using optimal control

We report on isotope selective three-photon ionization of two isotopomers of KRb by applying evolution strategies. The particularity of this experiment is based on the high resolution phase and amplitude modulation of the fs-laser pulses provided by a 2 × 640 pixel pulse shaper. The optimization in a closed feedback loop performed with spectrally broad pulses centered at 840 nm shows high enhancements of one isotopomer at the expense of the other isotopomer and vice versa. From the optimal laser field we aim to gain details about the selective ionization sequence and the wavepacket evolution on the involved vibrational states.     

Determination of radiative lifetimes of neutral sulphur by time-resolved three-photon VUV laser spectroscopy

Radiative lifetimes of the highly exited states s and d of neutral sulphur have been measured using time-resolved laser-induced fluorescence. The sulphur atoms were generated in a laser-produced plasma. The investigated states were populated through a two-step process involving a two-photon excitation to the lowest excited triplet state of even parity , followed by a one-photon excitation to the investigated state. We obtained ns and ns. These values are much longer than theoretically predicted ones and much shorter than those indirectely inferred from astronomical data. Received: 9 February 1998 / Accepted: 24 February 1998     

How to get access to long range states of highly excited molecules

Due to competition between ionic and covalent dissociation, the excited potential curves of the alkali dimers display long range structures, leading in some cases to secondary wells. We discuss the possibility of populating the well (with a depth of 1614.8 cm^-1, located at R _e = 30.5a ₀ ) that is present in the Na₂ potential curve and propose detection schemes. Received: 28 May 1998 / Revised: 5 August 1998 / Accepted: 24 September 1998     

Resonance enhanced multiphoton ionization (REMPI) and REMPI-photoelectron spectroscopy of ammonia

Resonance enhanced multiphoton ionization (REMPI) spectroscopy, preferably linked with kinetic energy analysis of the resulting photoelectrons (REMPI-photoelectron spectroscopy (PES)), continues to make enormous contributions to our understanding of the spectroscopy and, in many cases, the decay dynamics of small molecules in excited (normally Rydberg) electronic states. Here we present results of recent REMPI and REMPI-PES studies involving the ammonia molecule which provide further illustration of some of the many opportunities offered by these techniques. Received: 28 January 1998 / Revised: 3 April 1998 / Accepted: 15 April 1998     

On the finite-field transition dipole moment calculations by effective Hamiltonian methods

A simple finite-field scheme of calculations on electronic transition dipole moments in molecules by effective Hamiltonian methods is presented and discussed. The reliability of underlying approximations is analyzed by means of the quasidegenerate perturbation theory and corroborated by the results of pilot numerical applications. Received: 11 May 1998 / Revised and Accepted: 20 July 1998     

UV photoinduced dynamics in protonated aromatic amino acid

UV photoinduced fragmentation of protonated aromatic amino acids has emerged the last few years, coming from a situation where nothing was known to what we think a good understanding of the optical properties. We will mainly focus this review on the tryptophan case. Three groups have mostly done spectroscopic studies and one has mainly been involved in dynamics studies of the excited states in the femtosecond/picosecond range and also in the fragmentation kinetics from nanosecond to millisecond. All these data, along with high level ab initio calculations, have shed light on the role of the different electronic states of the protonated molecules upon the fragmentation mechanisms.     

Two-photon laser-induced fluorescence of H O and D O molecules at ambient pressure

We have carried out experiments of two-photon excitation of vapor phase H₂O and D₂O molecules at atmospheric pressure. A narrow-band tunable UV OPO laser is used in the experiments. Transient B ₁ → B ₁ emission from the excited predissociating state is seen in both cases. The complete B ₁ ← A ₁ fluorescence excitation spectrum in the spectral range of 245-250 nm is measured and compared with theory. It is shown that the predissociation rate increases with the rotational quantum number K' _a > 2 more strongly than with K ^′2 _a . No perturbation effects on the measured LIF spectra are observed at a laser power density below 2 GW/cm². Experimental results indicate a negligible contribution from both molecular association and collisions with atmospheric gases. Only an extremely weak vibrational progression belonging to the second positive system of N₂ has been observed, which appears to be due to energy and charge transfer in N ⁺ ₂ ^* + H ₂ O collisions. Received 25 January 2002 / Received in final form 27 May 2002 Published online 4 March 2003     

MJ and collision energy dependent attenuation of Rg (3P2) by CF3Br

The total attenuation cross-section of Rg (³P₂) (Rg = Ar, Kr) by the collision with CF₃Br is measured as a function of the magnetic sub level M_J of Rg (³P₂) and the collision energy. For Ar (³P₂), the attenuation process indicates a M_J dependence, in particular, the cross-section of the M_J = 0 state is lower compared with that for other states. On the other hand, Kr (³P₂) shows no M_J dependent attenuation.     

Classical study of and collisions in intense laser fields

In this paper, ion-atom and ion-ion collisions in the presence of intense laser fields are qualitatively studied by Classical Trajectory Monte Carlo (CTMC) simulations. It is found that in contrast to the field-free collisions, the colliding ion and the target nucleus could absorb energy from the applied laser fields when the electrons escape from the collision system. This result is explained in terms of Coulomb explosion induced by the enhanced ionization at the so-called critical internuclear distance. Also, the corresponding energy gain cross-sections are evaluated. Received: 7 October 1998 / Received in final form: 28 January 1999     

Ionization of a hydrogen atom from its ground state by a coherent bichromatic laser field

We study the “coherent phase control” between the three-photon ionization by a fundamental laser field and the one-photon ionization by its third harmonic for a hydrogen atom in its ground state. The relative phase δ of the harmonic field with respect to the fundamental laser radiation “modulates” the interference between the two ionization channels, which is important near the crossing points between the ionization rates of the two individual processes. Numerical results for the total ionization rate and for the angular distribution of the photoelectrons as a function of the phase δ are presented for frequencies located in the vicinity of the atomic resonances corresponding to the absorption of two laser photons. Received 31 August 2000 and Received in final form 6 February 2001     

Effects of the internuclear vector on the photoelectron angular distributions of H<Subscript>2</Subscript><Superscript>+</Superscript>

We study the photoelectron angular distributions (PADs) of diatomic molecule H₂ ⁺ irradiated by intense laser fields using a nonperturbative scattering theory. We find that the internuclear vector may change the PADs. The PADs have qualitative changes with the increasing of the internuclear distance. The molecular orientation affect the symmetry of the PADs. When the internuclear vector is vertical or parallel to the laser polarization vector, the PADs are four-fold symmetric; for other case the PADs are two-fold symmetric. Due to the modulation effect resulting from the molecular multi-core nature, the size of the jet and the main lobe can be enlarged or reduced. The molecular modulation effect become obvious for large internuclear distance.     

Magnetic trapping of strongly-magnetized Rydberg atoms

Effective magnetic moments of drift Rydberg atoms in strong magnetic fields are obtained for different energy and angular-momentum states. Classical two-body trajectory calculations and quantum-mechanical one-body calculations are employed. For heavy atoms such as rubidium, the trapping dynamics can largely be explained by the net magnetic moment due to the cyclotron and the magnetron motion of the Rydberg electron. In light Rydberg atoms such as hydrogen, the intrinsic two-body nature of the dynamics becomes manifest in that the ionic motion significantly contributes to the effective magnetic moment. Also, light drift Rydberg atoms exhibit an anisotropic response to field-inhomogeneities parallel and transverse to the magnetic-field lines. The results are relevant to magnetic trapping of Rydberg atoms in strong-magnetic-field atom traps.     

Picosecond time-resolved nonresonant ionization detected IR spectroscopy on 7-azaindole dimer

The picosecond time-resolved IR spectrum of the 7-azaindole dimer has been measured by picosecond time-resolved nonresonant ionization detected IR spectroscopy. This new time-resolved technique was developed by combining nonresonant ionization detected IR (NID-IR) spectroscopy with tunable picosecond IR and UV lasers. The time-resolved NID-IR spectrum from 2 600 cm^-1 to 3 800 cm^-1 shows a drastic change from 1.5 ps to 11 ps time evolution. A mode-specific vibrational redistribution has been suggested. Received 14 May 2002 / Received in final form 11 June 2002 Published online 13 September 2002     

Formation of Cs molecules via Feshbach resonances stabilized by spontaneous emission: theoretical treatment with the Fourier grid method

This paper proposes a general method to investigate Feshbach resonances in atomic collisions similar to Cs(6 s ) + Cs(6 p ) in the thermal or cold regime. In order to compute the predissociation widths of the C ¹ Π _u (6 s + 5 d ) bound vibrational levels of Cs₂, coupled both with the (2) ³ Σ ⁺ _u (6 s + 6 p ) continuum and with the (2) ³ Π _u (6 s + 5 d ) vibrational series, a Fourier grid method is implemented, with an optical potential. A convenient way of optimizing the latter is proposed. A large number of resonances are found and calculations of their cross-sections for stabilization into ground state molecules show that the rate may be important. This confirms the interpretation of Lintz and Bouchiat [Phys. Rev. Lett. 80, 2570 (1998)] who observed dimer formation in cell experiments. Possible generalization to the cold regime relies on the possibility to tune the position of a resonance to coincide with the maximum of the collisional energy distribution. Received 14 February 2002 Published online 28 June 2002