Photoionization cross-section measurements from the 2p, 3d and 3s excited states of lithium

The photoionization cross-sections from the 2p²P_{1/2, 3/2}, 3d²D_{3/2, 5/2} and 3s²S_1/2 excited states of lithium have been measured at different ionizing laser wavelengths, above the first ionization threshold. The experiments are performed by using a thermionic diode working in the space charge limited mode and the cross-sections are measured by employing the saturation technique. By changing the ionization photon energy, a smooth frequency dependence of the cross-sections has been observed for the 2p and 3d states. The cross-section from the 3s excited state has been measured at a single photon energy. The measured values of the photoionization cross are compared with the available data.     

Photodissociation dynamics of CF3I investigated by two-color femtosecond laser pulses

We report an experimental study of the multiphoton dissociation dynamics of CF₃I performed on a home-built femtosecond laser pump-probe system, with time-of-flight mass spectrometer. The first repulsive A band and the 5pπ³7sσ υ₂=1 Rydberg state of CF₃I were accessed by one- and two-photon transitions at 267 nm, respectively, with the latter two-photon absorption followed by a further two-photon probe transition at 401 nm to the state of the parent ion. The observed signals from the CF₃ ⁺ and I⁺ fragments show similar multi-component exponential decay patterns but the former is 4 times stronger than the latter. However, the parent CF₃I⁺ signal was observed to evolve in a very different manner, decreasing sharply when probed in the first 289 fs following excitation and subsequently rising again after 860 fs to a constant level below that measured at negative pump-probe delay times when the pump and probe pulses exchange roles. This dip observed in the parent ion profile, is very different from that previously reported at shorter pump wavelengths of 264 nm or 265 nm, and is interpreted as the competition between two different ionization channels. One from the vibrationally excited υ₂=1 of the irradiated Rydberg state and the other from the dissociative vibrational origin of the same electronic state which is populated by internal vibrational relaxation.     

Oscillator strength measurements of the 3p ↦ nd Rydberg transitions of sodium

We report new measurements of the oscillator strengths of the 3p ²P_3/2 ↦nd ²D_{5/2, 3/2} and 3p ²P_1/2 ↦ nd ²D_3/2 Rydberg transitions of sodium using a thermionic diode ion detector in conjunction with the Nd:YAG pumped dye lasers. The ns ²S_1/2 and nd ²D_5/2,3/2 Rydberg series have been recorded via two-step excitation, from the 3p ²P_3/2 and 3p ²P_1/2 intermediate states. Employing the saturation technique, the photoionization cross sections from the 3p ²P_3/2 and 3p ²P_1/2 intermediate states at the first ionization threshold are determined as 7.9(1.3) Mb and 6.7(1.1) Mb respectively. The f-values of the Rydberg transitions are calibrated with the photoionization cross section measured at the first ionization threshold and compared with the earlier data.     

Coherent population trapping involving Rydberg states in xenon probed by ionization suppression

We report the observation of pronounced coherent population trapping and dark resonances in Rydberg states of xenon. A weak two-photon coupling with radiation of = 250 nm is induced between the 5p^{6 1} S ₀ ground state of xenon and state 5p ⁵6p[1/2]₀, leading to (2+1) resonantly enhanced three-photon ionization. The state 5p ⁵6p[1/2]₀ is strongly coupled by radiation with ≃ 600 nm to 5p ⁵ ns[J _C]₁ or 5p ⁵ nd[J _C]₁ Rydberg states with principal quantum numbers n in the range 18 ?n? 23 and with the rotational quantum number of the ionic core J _C = 1/2 or J _C = 3/2. The ionization is monitored through observation of the photoelectrons with an energy resolution ΔE = 150 meV which is sufficient to distinguish the ionization processes into the two ionization continua. Pronounced and robust dark resonances are observed in the ionization rate whenever is tuned to resonance with one of the ns- or nd-Rydberg states. The dark resonances are due to efficient population trapping in the atomic ground state 5p^{6 1} S ₀ through the suppression of excitation of the intermediate state 5p ⁵6p[1/2]₀. The resolution is sufficient to resolve the hyperfine structure of the ns-Rydberg levels for odd xenon isotopes. The hyperfine splitting does not vary significantly with n in the given range. Results from model calculations taking the natural isotope abundance into account are in good agreement with the observed spectral structures. Pronounced dark resonances are also observed when the dressing radiation field with is generated from a laser with poor coherence properties. The maximum reduction of the ionization signal clearly exceeds 50%, a value which is expected to be the maximum, when the dip is caused by saturation of the transition rate between the intermediate and the Rydberg state due to incoherent radiation. This work demonstrates the potential of dark resonance spectroscopy of high lying electronic states of rare gas atoms. Received 7 May 2000 and Received in final form 25 June 2001     

Multiphoton ionization of CF<Subscript>3</Subscript>I clusters by ultraviolet laser radiation

The results of the investigation of the multiphoton ionization of (CF₃I) _n clusters by ultraviolet laser radiation are reported. The yields of the I₂⁺ and I⁺ ions, which are the products of the multiphoton ionization, have been measured as functions of the intensity of the ultraviolet radiation at the wavelengths of 308 and 232.5 nm. The degree of multiphoton ionization has been determined and appears to depend on the wavelength of radiation. The velocity distributions of the products have been measured in detail for various wavelengths and various polarizations of radiation. The anisotropy parameters of the velocity distributions of the produced ions and their kinetic energy have been determined. After analysis of the data, a mechanism of the multiphoton ultraviolet ionization of the clusters under investigation has been proposed. This mechanism depends on the used wavelengths.     

Reactions induced in (CF3I) n clusters by femtosecond UV laser pulses

The excitation and ionization of CF₃I molecules and their clusters by femtosecond UV laser pulses is studied. It is concluded that the types of excitation of free CF₃I molecules and their clusters by femtosecond UV laser pulses are different. The composition and kinetic energy of ion products observed upon the ionization of (CF₃I) _n clusters by femtosecond pulses are found to differ considerably from those obtained upon ionization by nanosecond pulses. It is shown that the molecular I ₂ ⁺ ion is produced in reactions induced in (CF₃I) _n clusters by UV radiation. Using the pump-probe method, we found the two channels of producing I ₂ ⁺ ions with characteristic times ??₁ ?? 1 ps and ??₂ ?? 7 ps. A model of the reactions under study proposed in the paper is consistent with our experimental results.     

Molecular dissociative sequential excitation and ionization of strontium vapor

We report new measurements on laser-assisted molecular dissociative sequential excitation and ionization spectra of strontium vapor. A single Nd:YAG pumped dye laser in conjunction with an atomic beam apparatus have been used to investigate the even parity 5snd ^3,1 D ₂ Rydberg series resulting from the 5s5p ¹ P ₁ resonance level. The relative intensities changes among the 5snd ³ D ₂ and ¹ D ₂ Rydberg series are attributed to the interactions with the 4d6s ^1,3 D ₂ perturbers, respectively. The interchannel interactions between the 5snd ¹ D ₂ series and the 4d6s ¹ D ₂ level and among the 5snd ³ D _1,2,3 series and the 4d6s ³ D _1,2,3 intruders have been separately parameterized using the two-channel quantum defect theory. Received: 10 September 1998 / Received in final form: 16 December 1998     

Ionization of Rydberg atoms in THz-laser fields at the transition from low to high scaled frequencies

We have studied the ionization of Rydberg-excited xenon atoms in THz-laser fields and by quantum dynamical calculations. The experimental threshold laser field strength for 10% ionization probability follows an n^*-1.68 (1.04 THz) dependence (n^* effective principal quantum number) with additional weak resonance structures and shows that ionization does not occur by a Landau-Zener mechanism. At scaled frequencies of to 5.6 the simulated threshold fields for ionization in oscillatory fields show a dependence on the principal quantum number n of n^-4.1 to n^-1.35. Received: 17 February 1998 / Revised: 20 April 1998 / Accepted: 21 April 1998     

Isotope shifts and hyperfine structure in calcium 4snp and 4snf F Rydberg states

Isotope shifts and hyperfine structure have been measured in 4snp ¹ P₁ and Rydberg states for all stable calcium isotopes and the radioisotope ⁴¹Ca using high-resolution laser spectroscopy. Triple-resonance excitation via Rydberg state was followed by photoionization with a CO₂ laser and mass selective ion detection. Isotope shifts for the even-mass isotopes have been analyzed to derive specific mass shift and field shift factors. The apparent isotope shifts for ⁴¹Ca and ⁴³Ca exhibit anomalous values that are n-dependent. This is interpreted in terms of hyperfine-induced fine-structure mixing, which becomes very pronounced when singlet-triplet fine-structure splitting is comparable to the hyperfine interaction energy. Measurements of fine-structure splittings for the predominant isotope ⁴⁰Ca have been used as input parameters for theoretical calculation of the perturbed hyperfine structure. Results obtained by diagonalizing the second-order hyperfine interaction matrices agree very well with experimentally observed spectra. These measurements allow the evaluation of highly selective and sensitive methods for the detection of the rare ⁴¹Ca isotope. Received 17 December 1999 and Received in final form 29 March 2000     

Polyatomic molecules formed with a Rydberg atom in an ultracold environment

We investigate properties of ultralong-range polyatomic molecules formed with a Rb Rydberg atom and several ground-state atoms whose distance from the Rydberg atom is of the order of n²a₀, where n is the principle quantum number of the Rydberg electron. In particular, we put emphasis on the splitting of the energy levels, and elucidate the nature of the splitting via the construction of symmetry-adapted orbitals.     

Multiphoton fragmentation and ionization of CF2HCl molecules and clusters by UV radiation

The results of experimental studies of multiphoton ionization of CF₂HCl molecules and clusters by UV laser radiation in the wavelength range 217–236 nm are reported. In the case of molecules, the main reaction products are CF₂H⁺ and CF⁺ ions as well as atomic chlorine. It is found that the spectra of the products of ionization of free molecules and molecules condensed into clusters differ qualitatively: multiphoton ionization of clusters does not yield CF₂H⁺ ions. The dependences of the ion yield on the intensity of laser radiation and its wavelength are measured. The effect of a constant electric field and the radiation spectral width on the multiphoton ionization process is demonstrated. The shape of the velocity distributions is determined for a number of products. A strong anisotropy is detected in the reaction of formation of CF₂H⁺ ions. Possible mechanisms for these processes are discussed.     

Influence of the helium autoionization structures on the single/double ionization signal

Calculations of intense field (around 10¹⁶ W/cm²) single- and double-ionization processes in helium at XUV wavelengths are presented. The laser wavelength is chosen near the | 2s2p ¹ P autoionization structure and the dynamics are explored. Single and double ionization yields, as well as the photoelectron energy spectrum for photon energies around the autoionization structure are calculated. In the case of a pulse of few femtoseconds duration, no significant enhancement of the double ionization yield has been found in tuning the photon frequency around the peak of the resonance. It is also shown that in the case of a long pulse (and hence narrow compared with the relevant autoionization width), the branching ratio of double to single ionization yield can be relatively enhanced by tuning to the absorption minimum of the resonance. Received 19 February 2002 / Received in final form 2 May 2002 Published online 19 July 2002     

Dynamics of resonant energy transfer in a cold Rydberg gas

We investigate excitation transfer and migration processes in a cold gas of rubidium Rydberg atoms. Density-dependent measurements of the resonant population exchange for atoms initially excited into the 32P_3/2(|m_J|=3/2) state are compared with a Monte Carlo model for coherent energy transfer. The model is based on simulations of small atom subensembles involving up to ten atoms interacting via coherent pair processes. The role of interatomic mechanical forces due to the resonant dipole-dipole interaction is investigated. Good agreement is found between the experimental data and the predictions of the model, from which we infer that atomic motion has negligible influence on the energy transfer up to Rydberg densities of 10⁸ cm^-3, that the system has to be described in terms of many-body dynamics, and that the energy transfer preserves coherence on microsecond timescales.     

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     

Reactions of excited I*(2P1/2) and unexcited I(2P3/2) iodine atoms in perfluoroalkyl radicals

A method of investigating reactions of excited and unexcited atoms is discussed. It is based on pulsed photolysis of molecules with simultaneous passage of laser radiation through the working medium. The method proposed is used to investigate the reactions that accompany the photolysis of the molecules RI(CF₃I, n-C₃F₇I, i-C₃F₇I). The rate constants of the recombination of iodine atoms into I₂ in the presence of RI molecules are calculated for the atoms I(²P_3/2) and I*(²P_1/2), as are the recombination constants of the radicals R into R₂ and with the atoms I*(²P_1/2) and I(²P_3/2) into the RI molecule. It is shown that the I(²P_3/2) atoms are much more active in the recombination into Ia and RI than the I*(²P_1/2) atoms. The role of the investigated reactions in the kinetics of a photodissociation iodine laser (PDIL) is discussed. The results are compared with the published data.     

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.     

Possibility of separating the isotopes127I and129I with the aid of a photodissociation iodine laser

A method for separating iodine isotopes is proposed, based on the large difference between the rate constants of the excited I*(²P_1/2) and unaxclted iodine atoms with radicals CF₃ and with Cl₂ molecules, and on the possibility of selectively acting on the₁₂₇I atoms in the states²P_1/2 and²P_3/2 by radiation from a photodissociation R¹²⁷I iodine laser (λ = 1.315 μm). The possibility of separating the pure isotope¹²⁹I and the mixture¹²⁷I with¹²⁹I is investigated.     

Multiphoton dissociation of CF<Subscript>3</Subscript>I clusters by IR laser radiation

The results of investigation of dissociation of (CF₃I) _n clusters upon resonant excitation of vibrations of CF₃I molecules by pulsed CO₂ laser radiation are reported. The kinetics of dissociation of such clusters is studied and the dissociation yield is measured. It is shown that its value is completely controlled by fluence Φ_IR of transmitted IR radiation energy and its time dependence is exponential. The results of measurements show that the dissociation lifetime of clusters is shorter than 10^?8 s. The velocity and translational temperature of free CF₃I molecules formed during dissociation of clusters are measured, as well as the dependence of these parameters on Φ_IR. It is concluded that, under these conditions of IR excitations, the dissociation of (CF₃I) _n clusters can be treated as consecutive evaporation of molecules.     

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     

Two-step laser excitation of the highly excited even-parity states of atomic mercury

We report term energies and quantum defects of highly excited even-parity states of mercury in the 83 876–84 140 cm^-1 energy range, employing a two-step laser excitation scheme via the S₀↦6s6p³P₁ inter-combination transition. Two dye lasers, pumped by a common Nd:YAG laser, were frequency doubled by BBO crystals and used to record the spectra in conjunction with a thermionic diode ion detector. Our new observations include the much extended D₂ (22 ≤n ≤52) series and a few members of the S₁ (24 ≤n ≤30) Rydberg series. Members of the D₂ Rydberg series with such a high n value are reported for the first time. The relative intensities of the D₂ and S₁ transitions (m = 4, 5 and 6) of group II-B elements excited from the P₁ inter-combination states are also discussed.