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)     

Electron-beam-induced fluorescence of carbon dioxide clusters. II. Molecular beam with clusters

The fluorescence of CO₂ clusters excited by an electron beam in a molecular beam formed from a free jet expansion of carbon dioxide is investigated. Data on the fluorescence of the clusters are obtained by comparing the electron-beam-induced fluorescence with the signal appearing in an electronic-fluorescence detector as a result of reflection of the cluster beam from an obstacle placed after the electron beam, as well as with the intensity of the cluster beam. It is established that, unlike a jet expansion, for CO₂ clusters in a molecular beam the fluorescence yield from a cluster decreases significantly with increasing cluster size and is very small for clusters of large size. It is concluded on the basis of the results from an investigation of the fluorescence of CO₂ clusters that the electron-beam-induced fluorescence technique can be used for measurements in molecular beams with CO₂ clusters. Zh. Tekh. Fiz. 67, 63–71 (July 1997)     

Measurement of nanoparticle temperature in a (CO2) N cluster beam using SF6 molecules as tiny probe thermometers

A temperature measurement technique using SF₆ molecules as tiny probe thermometers is described, and results are presented, for large (CO₂) _N van der Waals clusters (with N ≥ 10²) in a cluster beam. The SF₆ molecules captured by (CO₂) _N clusters in crossed cluster and molecular beams sublimate (evaporate) after a certain time, carrying information about the cluster velocity and internal temperature. Experiments are performed using detection of these molecules with an uncooled pyroelectric detector and infrared multiphoton excitation. The multiphoton absorption spectra of molecules sublimating from clusters are compared with the IR multiphoton absorption spectra of SF₆ in the incoming beam. As a result, the nanoparticle temperature in the (CO₂) _N cluster beam is estimated as T _cl < 150 K. Time-of-flight measurements using a pyroelectric detector and a pulsed CO₂ laser are performed to determine the velocity (kinetic energy) of SF₆ molecules sublimating from clusters, and the cluster temperature is found to be T _cl = 105 ± 15 K. The effects of various factors on the results of nanoparticle temperature measurements are analyzed. The potential use of the proposed technique for vibrational cooling of molecules to low temperatures is discussed.     

Universal probe method for measuring the temperature of large clusters (nanoparticles) in a cluster beam

A universal probe method for measuring the temperature of large clusters (nanoparticles) in a cluster beam has been proposed and experimentally implemented. The temperature of large van der Waals clusters (nanoparticles) (CO₂) _N (where N ⩾ 10² is the number of monomers in a cluster) in the cluster beam is measured using this method with SF₆ molecules as miniature probe thermometers. The SF₆ molecules are captured by the (CO₂) _N clusters in intersecting cluster and molecular beams and sublimate from the surface of the clusters, carrying information on the velocity and temperature (internal energy) of the clusters. The velocity (kinetic energy) of SF₆ molecules sublimating from the surface of the clusters has been measured by the time-of-flight method and the temperature of the clusters has been determined as T _cl = (105 ± 15) K.     

Investigation of atomic and molecular clustering in a pulsed gas-dynamic jet with a pyroelectric detector

The clustering of atoms and molecules in a pulsed gas-dynamic jet has been investigated by the method of time-of-flight measurements performed with an uncooled pyroelectric detector (PED). The method is based on measuring the amplitude of the pyroelectric signal induced on the detector by a molecular (atomic) beam and the particle velocity in the beam as a function of the gas pressure above the nozzle. In addition, the number of molecules (atoms) emerging from the nozzle in a pulse has been measured. We describe the method and present the results of our studies on the clustering of He, Xe, CH₄, CO₂, and other gases. The peculiarities of the detection of molecular and cluster beams with PED are considered. We show that the described method allows the clustering threshold as a function of the gas pressure above the nozzle to be determined. We have established the threshold pressures at which particle clustering in the jet begins. Optimal conditions for the generation of intense cluster beams have been found.     

Detection of SF<Subscript>6</Subscript> molecules sublimating from the surface of (CO<Subscript>2</Subscript>)<Subscript><Emphasis Type="Italic">N</Emphasis></Subscript> nanoparticles in a cluster beam by the infrared multiphoton excitation method

It has been found that SF₆ molecules captured by large van der Waals clusters (CO₂) _N (where N ≥ 10² is the number of monomers in a cluster) in intersecting molecular and cluster beams sublimate from the surface of clusters after a certain time and carry information on the velocity and temperature (internal energy) of clusters. Experiments have been carried out for detecting these molecules by means of a pyroelectric detector and the infrared multiphoton excitation method. The multiphoton absorption spectra of molecules sublimating from the surface of clusters have been obtained. The temperature of the (CO₂) _N nanoparticles in the cluster beam has been estimated using these spectra and comparing them with the infrared multiphoton absorption spectra of SF₆ in the initial molecular beam.     

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     

Selecting molecules embedded in nanodroplets (clusters) of superfluid helium

A method of selecting molecules embedded in nanodroplets (clusters) of superfluid helium is proposed, which is based on the selective vibrational excitation of embedded molecules by intense IR laser radiation. This action leads to a significant decrease in size of the excited clusters, after which these clusters are separated with respect to size via scattering of the cluster beam on a crossing atomic beam. The method is described in detail and the possibility of selecting SF₆ molecules in liquid helium nanodroplets using the excitation by CO₂ laser radiation and the angular separation via scattering on a xenon atomic beam is demonstrated. The results show that, by using this technique, it is possible to separate molecules with respect to isotope (element) composition. Advantages and drawbacks of the method are analyzed.     

Temperature determination of (CF<Subscript>3</Subscript>I)<Subscript><Emphasis Type="Italic">N</Emphasis></Subscript> clusters in a beam by time-of-flight measurements of IR-laser excited SF<Subscript>6</Subscript> molecules sublimating from the surface of clusters

The method is described and the experimental results are presented on the temperature determination of the (CF₃I) _N clusters in a beam (N ⩽ 10² is a number of monomers in a cluster) using SF₆ molecules from intersecting molecular beam as probe thermometers. The SF₆ molecules are captured by clusters in the crossed cluster and molecular beams and, after a certain time, sublimate from the surface of clusters carrying information on the velocity and temperature (internal energy) of clusters. Using time-of-flight (TOF) method the kinetic energy (velocity) of sublimated SF₆ molecules was measured and the temperature of clusters was determined to be T _cl = (88 ± 15) K.     

Formation and measurement of cluster beams at gasdynamic cooling of CF2HCl molecules

The clustering of CF₂HCl (Freon-22 refrigerant) molecules is found to take place when these molecules are dynamically cooled in a pulsed supersonic beam. A method of CF₂HCl cluster beam diagnostics is developed that combines UV multiphoton ionization, time-of-flight mass spectroscopy, and cluster IR photodissociation. The velocity of directed motion of (CH₂HCl)_n clusters, as well as the longitudinal and transverse velocities of their thermal motion, are measured at different stagnation pressures P ₀. The cluster mean size and the degree of clustering in the flow are estimated depending on supersonic flow conditions.     

A gas cluster ion beam accelerator

An assembled CO₂ gas cluster ion beam system was assessed using a retarding field analyzer and a time-of-flight mass spectrometer. The CO₂ gas was expanded to form gas clusters at the input pressure of 1–5 bar through a quartz Laval nozzle. At 4 bar, it is confirmed that the clusters consisted of about 500 molecules. Also the dependence of the mean cluster size distribution on source temperature was examined. At the low fluence of ion beam, an isolated gas cluster ion impact on solid surfaces was investigated. CO₂ gas cluster ions were irradiated at the acceleration voltage of 40–60 kV on highly oriented pyrolytic graphite. Si with native oxide layers, and Cu film deposited on Si wafer. After very short exposure of cluster ions, induced hillocks with about 0.8–1 nm in height and 20 nm in width were outgrown from the impacted surfaces. After prolonged irradiation on Si and Cu/Si, humping was more developed and consequently the surface morphology seemed to be saturated because of gradual filling the gap between the hillocks.     

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.     

Molecular beam deflection experiments on mixed clusters

Gas phase Ti-C₆₀ clusters are studied by molecular beam electric deflection. The permanent dipole moment of the TiC₆₀ molecule is determined. It is equal to 8.1±1.5 D. This dipole is due to a transfer of electron from the transition metal atom to the C₆₀ cage. No dipole is observed for Ti(C₆₀)₂ molecules. This is in agreement with the symmetrical dumbbell-like structure that has been previously proposed. Received 22 November 2000     

Calculation on the CO2 influences on the structure,stability of (MgO)m (m = 1–6) clusters

ABSTRACT

The concentration of carbon dioxide (CO₂) has a significant influence on the morphology of thermal decomposition products of magnesite. So, structures, stabilities and adsorption mechanisms of (MgO)_m (m?=?1–6) clusters by one or two CO₂ molecules were calculated by the GGA-PW91 method. The results show that the stability of the considered clusters is (MgO)_m(CO₂)₂ clusters > (MgO)_m(CO₂) clusters > (MgO)_m clusters by the average binding energy. Certain low-lying isomers of (MgO)_m(CO₂) and (MgO)_m(CO₂)₂ clusters which have an isolated O atom are deviating from the cluster center which possess higher kinetic activity. (MgO)_m clusters prefer to adsorb a CO₂ molecule, while (MgO)₃(CO₂) clusters prefer to adsorb a CO₂ molecule rather than the neighbors. Magnesite is difficult to transit to (MgCO₃)₂ clusters at room temperature. However, magnesite will spontaneously transit to (MgO)₂ clusters and further transit to MgO crystal which need to adsorb more energy at 700?K.     

Diagnostics of pulsed molecular beams and free jets with pyroelectric detectors and TEA CO2 lasers

A pyroelectric detector with a time resolution of 3–5 s and a TEA CO₂ laser have been used in diagnostics of a pulsed molecular beam (a free jet). The kinetic energy distribution of molecules was determined by using time-of-flight measurements both with a laser and without it. A combination of the laser with the pyroelectric detector makes it possible to determine the kinetic energy distribution of molecules in a selected internal state and to measure the energy absorted by the molecules of the beam from a laser pulse. The results obtained for pure SF₆ and the SF₆ seeded in He have been presented and analyzed. The advantages and the disadvantages of the method are being discussed in comparison with other available methods of diagnostics of molecular beams and free jets.     

Hydrated clusters of organic molecules generated by IR OPO resonant desorption of frozen aqueous solutions

Long series of hydrated clusters of organic molecules (formaldehyde, methanol, ethanol and tryptophan) have been generated by infrared optical parametric oscillator (OPO) resonant desorption of frozen aqueous solutions. Using a comparative approach, we derived some general trends from cluster size and velocity distribution measurements. In the biologically interesting case of tryptophan amino acid, our technique yields a much longer (and complete) series of hydrated clusters than that obtained previously using a combined laser desorption/pulsed jet expansion technique [L.C. Snoek, R.T. Kroemer, J.P. Simons: Phys. Chem. Chem. Phys. 4, 2130 (2002)]. PACS 79.20.La; 36.40.-c; 82.80.Ms     

Nanofriction studies of reactively or non-reactively cluster-eroded single crystal diamond

Friction properties of cluster-eroded surfaces of synthetic single crystal diamond (Monodite) are compared after erosion with high-speed CO₂ cluster beams as well as with corresponding Ar cluster beams, the cluster impact kinetic energy being 100 keV in both cases. The respective friction values are determined by atomic force microscope measurements. Using CO₂ clusters, the reactive accelerated cluster erosion (RACE) of the single crystal diamond substrates leads to more than seven times higher friction values than those observed after erosion with non-reactive accelerated Ar clusters. Molecular dynamics calculations reveal related differences in the simulations of respective single cluster impacts already at 2 ps after impact.     

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).     

Adsorption of small molecules on transition metal doped rhodium clusters Rh3X (X = 3d, 4d atom): a first-principles investigation

The adsorption behaviours of seven molecules (CO, CO₂, N₂, NO, O₂, N₂O and NO₂) on Rh₃X (X?=Sc-Zn, Y-Cd) clusters are systematically investigated by density-functional calculations. Rh₃X clusters exhibit physical adsorption when interacting with CO₂, CO, N₂ and NO. The adsorption energies (E_ads) can be ranked as follows: NO?>?CO?>?CO_2?≥?N₂. Compared with pure Rh₄ cluster, the adsorption capacity changes with the doping element. Chemical adsorption can be obtained for Rh₃X when adsorbing O₂, N₂O and NO₂. E_ads shows an order of E_ads(O₂)?>?E_ads(NO₂)?>?E_ads(N₂O). When O₂ is adsorbed, energy barrier with doping Tc or Cr atom is substantially reduced, which indicates that chemical reactivity of O₂ on Rh₄ can be significantly enhanced. The doped rhodium clusters can be viewed as good candidates in the discrimination between different gas molecules.