A study of the global chirp dependence on the interaction of intense colored double pulses with clusters

The yields of highly charged atomic ions produced in the exposure of xenon clusters embedded in helium nanodroplets by intense colored double pulses show a notable sensitivity on the order of the subpulses. The only slight difference in their spectral composition leads to a flipping of the optimal laser parameters for effective multielectron ionization above certain charge states, which appears to be quite robust with respect to the chosen pulse fluence and reflects an avalanche-like developing cluster ionization scenario.     

The effect of volumetric weighting in the interaction of intense laser fields with clusters

Silver clusters embedded in helium nanodroplets are exposed to intense femtosecond laser pulses (10¹³ - 10¹⁶ W/cm²). The signal of highly charged (q≤11) atomic fragments is maximized by delayed plasmon enhanced ionization using stretched laser pulses. Further details with respect to the dynamics of the charging process can be obtained, when the intensity distribution within the laser focus is taken into account. For the first time, the z-scan method is applied to clusters which offers a route to investigate the explicit dependence of the ion signals with respect to the laser intensity. By taking advantage of the volumetric weighting effect ionization thresholds are determined, yielding values well below 10¹⁴ W/cm² for Ag^q+ ions with q≤11.     

Tunable diode laser spectroscopy of helium clusters

Helium clusters, He_N-X, containing a probe molecule, X, are studied by infrared spectroscopy for the size range N≈1∼100. Spectra are observed using a supersonic jet expansion and a tunable diode laser source operating in a rapid-scan (sweep integration) mode. The pulsed jet uses a dilute gas mixture of the probe molecule in helium, with relatively high backing pressures (5–50 bar), and a cooled (80–295 K) nozzle. Sensitivity is enhanced by multi-passing the laser beam through the jet with a toroidal mirror system. The clusters are larger than van der Waals dimers and trimers, but smaller than those encountered in the field of helium nanodroplets (N≈10³–10⁵). Furthermore, individual cluster sizes are resolved here, but not with nanodroplets, and infrared absorption is detected directly (change in transmitted laser intensity), rather than indirectly (change in cluster fragmentation). Trends in the spectra are described for five probe molecules, X=CO, SiH₄, OCS, N₂O, and CO₂. Superfluid effects dominate for clusters larger than N≈8. Notable results include the unexpected observation of broad oscillations in the effective rotational constants as a function of cluster size. PACS 33.20.Ea; 34.30.+h; 36.40.Mr; 42.55.Px     

Interaction of intense beams of highly vibrationally excited molecules with molecules (clusters) condensed on a cold surface

The interaction of intense beams of SF₆ and CF₃I molecules, excited by powerful IR laser radiation to high vibrational states (0.3 eV ≤ E _vib ≤ 2.0 eV), with molecules (clusters) condensed on a cold surface (T _s ≈ 80–85 K) has been studied. The probability that the excited and unexcited molecules are reflected from the cold metal surface covered by condensed molecules (clusters), as well as the probability that such excited and unexcited molecules are transmitted through a cooled multichannel metal plate and a converging cone oriented at an angle relative to the molecular beam axis, has been determined. Expressions for these probabilities of reflection and transmission as functions of the angle of incidence and the parameters of the exciting laser radiation and the molecular beam are obtained. It is shown that highly vibrationally excited molecules are reflected from the surface and transmitted through the plates and cones with a much higher probability than unexcited molecules. The results suggest that this phenomenon can be used for the separation of molecules in a beam with respect to isotope (or atomic) composition.     

Two-step excitation of Rb atoms on He nanodroplets

We present the first sequential laser excitation of atom-doped helium nanodroplets. Rubidium atoms on the surface of helium nanodroplets are selectively excited with a continuous wave laser to the 5²P_1/2 state so as not to desorb from the nanodroplets. From there they are excited by a laser pulse to the 5²D state; a laser-induced fluorescence (LIF) spectrum is recorded by monitoring the 6²P ?\rightarrow 5²S_1/2 emission. The LIF spectrum differs from that of the two-photon one-color direct excitation spectrum 5²D ?\leftarrow 5²S_1/2, indicating that the system does relax vibrationally during the lifetime of the 5²P_1/2 state. To model the LIF spectra we use calculated energy levels of the Rb atom as a function of its distance R from the center of the helium nanodroplet. The Franck-Condon factors of the resulting potential energy curves agree with the experimental spectra. In the future the 5²P_1/2 state can be used as a springboard to reach high-lying ²S and ²D states, and possibly create an artificial super-atom.     

Mass spectrometric investigation of anions formed upon free electron attachment to nucleobase molecules and clusters embedded in superfluid helium droplets

Here we report the first mass spectrometric study of negative ions formed via free electron attachment (EA) to nucleobases (NBs) embedded in helium clusters. Pure and mixed clusters of adenine and thymine have been formed by pickup of isolated NB molecules by cold helium droplets. In contrast to EA of isolated molecules in the gas phase we observe a long-lived parent anion NB- and, in addition, parent cluster ions NB-n up to size n=6. Moreover, we show that a low energy electron penetrating into a doped helium droplet causes efficient damage of the embedded nucleobases via resonant, site selective, dissociative electron attachment.     

Stability of two-component alkali clusters formed on helium nanodroplets

The stability of two-component clusters consisting of light (Na or K) and heavy (Rb or Cs) alkali atoms formed on helium nanodroplets is studied by femtosecond laser ionization in combination with mass spectrometry. Characteristic stability patterns reflecting electron shell-closures are observed in dependence of the total number of atoms contained in the mixed clusters. Faster decay of the stability of mixed clusters compared to the pure light ones as a function of size indicates a destabilizing effect of heavy alkali atoms on light alkali clusters, presumably due to second order spin-orbit interaction.     

Changing the fragmentation pattern of molecules in helium nanodroplets by co-embedding with water

Individual amino acid molecules embedded in helium nanodroplets fragment extensively when the beam is ionized by electron bombardment. However, we find that when glycine and tryptophan are picked up right after, or right before, a small amount of water, the mass spectra become significantly altered. For glycine, the detected ions consist almost entirely of intact protonated amino acids, with or without a few water molecules attached. In other words, the presence of water exerts a striking “buffering” effect on the ionization-induced fragmentation. For tryptophan the effect is weaker but also present. In both cases, the hydroxyl group lost upon ionization overwhelmingly comes from the water partner (in strong contrast to the situation observed when amino acids are picked up by neat water clusters). A complementary experiment involving DCl molecules co-embedded with water shows that in this case Cl and/or DCl invariably leave the droplet upon ionization. The observed patterns may be steered by the analytes' dipole moments or by solvation effects.     

Nonclassical rotations of single molecules in small helium and hydrogen clusters: Manifestation of “microscopic superfluidity”

The studies of small helium clusters (up to 100 atoms) and molecular-hydrogen clusters (up to 20 molecules) that are formed in a supersonic gas jet and are coupled by the weak van der Waals interaction with a linear chromophore molecule are reviewed The shift of the frequency of the fundamental vibration of the chromophore, as well as a change in the moment of inertia of a cluster with its growth, has been detected by their rotational and vibrational-rotational spectra. A nonclassical behavior of the moment of inertia manifested in its decrease beginning with a certain number of attached He atoms (H₂ molecules) has been revealed. This behavior indicates that a part of a cluster is decoupled from the rotational motion of a molecule. The key question of these studies is whether such behavior of the moment of inertia is the manifestation of the super-fluidity of helium and hydrogen at microscopic level. The results are compared to the spectroscopy of molecules and hydrogen clusters in liquid-helium nanodroplets.     

Electron-induced fluorescence of carbon dioxide clusters. I. Free jet of condensing gas

In measurements in jets of condensing gases, problems arise in interpreting the results obtained with the use of electron-beam fluorescence diagnostics, in particular due to the possible contribution of clusters to the radiation from the jet. Data on the fluorescence are obtained by comparing the optical and x-ray emission excited by an electron beam with calculations of the amount of condensate. Studies are made on the fluorescence of CO₂ clusters excited by an electron beam in a free jet of the condensing carbon dioxide gas. It is found that the clusters radiate at wavelengths of the monomers extremely effectively per molecule, almost as much as the free molecules, and the dependence on size is quite weak. It is shown that with electron-impact excitation the emission of the clusters comes about as the result of the ejection of excited molecules from the cluster as the latter fragments. The results of this investigation of the fluorescence of CO₂ clusters lead to conclusions regarding the use of electron beam fluorescence diagnostics for measurements in free jets with CO₂ clusters. Zh. Tekh. Fiz. 67, 43–52 (March 1997)     

Formation of cold bialkali dimers on helium nanodroplets

Cold alkali diatomic molecules (LiCs, NaCs) in the lowest vibrational state of the electronic triplet ground state are formed on superfluid helium nanodroplets. Using photoionization detection the excitation spectra of the transitions are recorded. The splitting of the vibrational structure in the LiCs spectrum, not observed in the NaCs spectrum, is interpreted in terms of molecular fine structure. The spectra are well reproduced by a model based on quantum chemistry potential curves including spin-orbit coupling, in combination with an asymmetric line shape function to account for cluster-induced broadening. Our refined potential curves provide important input data for the photoassociation of ultracold dipolar alkali molecules from atomic quantum gases.Received: 1 July 2004, Published online: 26 October 2004PACS: 36.40.Mr Spectroscopy and geometrical structure of clusters - 34.50.Gb Electronic excitation and ionization of molecules; intermediate molecular states (including lifetimes, state mixing, etc.) - 33.20.-t Molecular spectra     

Precision lifetime measurement of fine structure states in the NeI 2p53p configuration

The beam—gas-laser two-step excitation technique of a fast ion beam is used for precision measurements of atomic life-times. By observing the decay of the purely laser induced fluorescence radiation, the lifetimes of eight fine-structure levels 2p₂ to 2p₉ in the NeI 2p⁵3p configuration were measured with total standard deviations of 0.2 to 0.5%.     

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.     

Energy accommodation and reactivity of O2 on tungsten

We have determined by direct molecular beam velocity measurements that translational energy accommodation of O₂ molecules scattered from a hot polycrystalline tungsten target is inefficient at high surface temperatures. Translational energy accommodation is inefficient whether the surface is clean or covered with oxygen to a varying extent, even though in the latter case the scattering is diffuse. On a clean tungsten surface the scattering of the O₂ was approximately specular and the reaction probability of O₂ was constant and greater than 90% over the temperature range 1000K to 2800 K. It was shown by simultaneous helium scattering that atomic surface roughness of an oxygen chemilayer, rather than trapping, is a major cause of the observed diffuse scattering of oxygen. At the lowest surface temperature of 1000 K, with an oxygen chemilayer present, the velocity of the most probable number density of the scattered O₂ was lower than in the incoming beam or than that expected for complete equilibration with the surface.     

The internal energy of small ammonia clusters in a supersonic beam and after scattering off LiF(100)

The photoionization efficiency (PIE) of neutral ammonia clusters is studied as a function of photon energy. From these curves the internal energies of clusters in the incident supersonic beam and of clusters surviving after scattering off a LiF(100) surface are derived. A supersonic expansion of ammonia seeded in He produces small clusters of various size but with uniform kinetic energy of about 285 meV per monomer molecule. The mass distribution of clusters in the jet and of the scattered particles is measured in a reflecting time-of-flight mass spectrometer by single photon photoionization using vacuum ultraviolet (VUV) laser radiation tunable between and . In the incident beam the internal energies of clusters up to n = 15 do not vary significantly and amount to an average of about . After scattering off LiF(100) the internal energy of clusters up to n = 4 increases with fragment size and amounts to about half a monomer binding energy. Received 18 October 1999 and Received in final form 10 December 1999     

IR Laser Control of the Clustering of CF<Subscript>3</Subscript>Br Molecules during the Gas-Dynamic Expansion of a CF<Subscript>3</Subscript>Br/Ar Mixture: Bromine Isotope Selectivity

The infrared (IR) laser radiation control of the clustering of CF3Br molecules during the gas-dynamic expansion of a CF₃Br/Ar mixture at the exit from a nozzle is investigated. Prominence is given to studying the possibility of bromine-isotope-selective suppression of the clustering of CF₃Br molecules due to their resonance vibrational excitation in the gas-dynamic expansion zone near the nozzle. A continuous CO₂ laser is used in experiments to excite molecules and clusters in a beam, and a quadrupole mass spectrometer is used to detect them. The experimental setup and the experimental technique are described. The dependences of the efficiency of molecule clustering suppression on the exciting laser radiation parameters, the gas parameters (composition, pressure) above the nozzle, and the distance from the nozzle exit section to a molecule irradiation zone are obtained. Bromine-isotope-selective suppression of molecule clustering is shown to occur at the exit from the nozzle due to the resonance vibrational excitation of gas-dynamically cooled CF₃Br molecules. When CF₃Br/Ar mixtures are used at pressure ratios p(CF₃Br): p(Ar) = 1: 10 and 1: 30, the enrichment of a cluster beam by bromine isotopes are K_enr(⁸¹Br) ≈ 1.18 ± 0.09 and 1.12 ± 0.07 during the 9R(30) laser line (1084.635 cm^–1) irradiation of a jet. The clustering suppression selectivity is α ≈ 1.18 when the mixture at the pressure ratio p(CF₃Br): p(Ar) = 1: 10 is used. These results suggest that the proposed method can selectively control the clustering of the molecules containing the heavy element isotopes that have a small isotope shift in IR absorption spectra (OsO₄, WF₆, UF₆).     

Fragmentation of dodecanethiol molecules: application to self-assembled monolayer damage in atom lithography

Atom lithography commonly employs self-assem- bled monolayers (SAMs) of alkanethiols which act as resists to protect prepared surfaces. Metastable atomic species such as helium are used to damage the resist, enabling pattern transfer via mask lithography, followed by wet chemical etching. The damage mechanism is, however, not well understood. Here we report studies of fragmentation of dodecanethiol (DDT) molecules embedded in helium nano-droplets that have been irradiated by an electron beam. The results of the charge-transfer fragmentation process provide the first experimental data on the damage mechanisms that occur in the metastable helium/SAM interaction. Received: 20 September 1999 / Revised version: 6 December 1999 / Published online: 8 March 2000     

Femtosecond ionization of magnesium clusters grown in ultracold helium droplets

Magnesium clusters grown in helium droplets and ionized with femtosecond laser pulses have been studied by high resolution mass spectrometry. For moderate laser intensities the abundance spectra show characteristic features indicating electronic shell effects. Compared to clusters of s¹-electron metals additional shell closures appear resulting from an electron rearrangement. Irradiation with higher laser intensities leads to a decomposition of the magnesium clusters into atomic ions. Due to charge exchange with the surrounding helium matrix mainly singly and doubly charged magnesium ions remain. In addition, the occurrence of MgHe_N ⁺-complexes is observed. Their abundance depends on the shape of the laser field, i.e. the laser width and the optical delay when applying the pump-probe technique. Received 2 January 2001     

The formation of an intense secondary pulsed molecular beam and obtaining accelerated molecules and radicals in it

A method for obtaining an intense secondary pulsed molecular beam is described. The kinetic energy of molecules in the beam can be controlled by vibrational excitation of the molecules in the source under high-power IR laser radiation. A compression shock (shock wave) is used as a source of secondary beams. The shock wave is formed in interaction between an intense pulsed supersonic molecular beam (or flow) and a solid surface. The characteristics of the secondary beam were studied. Its intensity and the degree of gas cooling in it were comparable with the corresponding characteristics of the unperturbed primary beam. Vibrational excitation of molecules in the shock wave and subsequent vibrational-translational relaxation, which occurs when a gas is expanded in a vacuum, allow the kinetic energy of molecules in the secondary beam to be substantially increased. Intense [≥10²⁰ molecules/(sr s)] beams of SF₆ and CF₃I molecules with kinetic energies approximately equal to 1.5 and 1.2 eV, respectively, were generated in the absence of carrier gases, and SF₆ molecular beams with kinetic energies approximately equal to 2.5 and 2.7 eV with He (SF₆/He=1/10) and H₂ (SF₆/H₂=1/10) as carrier gases, respectively, were obtained. The spectral and energy characteristics of acceleration of SF₆ molecules in the secondary beams were studied. The optimal conditions were found for obtaining high-energy molecules. The possibility of accelerating radicals in secondary molecular beams was demonstrated.     

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.