Generation of CW cold CH3CN molecular beam by a bent electostatic quadrupole guiding: Monte-Carlo study

A new kind of continuous-wave (CW) cold molecular beam, methyl cyanide (CH₃CN) beam, is generated by a bent electrostatic quadrupole guiding. The Stark shift of rotational energy levels of CH₃CN molecule and its population distribution are calculated, and the dynamic processes of electrostatic guiding and energy filtering of CH₃CN molecules from a gas source with room temperature (300 K) are simulated by Monte Carlo Method. The study showed that the longitudinal and transversal temperatures of output cold CH3CN beam could be about ～2 K and ～ 420 mK, and the corresponding guiding efficiency was about 10^?5 as the guiding voltage was 3 kV. Furthermore, the temperature of the guided molecules and its guiding efficiency can be controlled by adjusting the guiding voltages applied on electrodes.     

Generation of CW cold CHCN molecular beam by a bent electostatic quadrupole guiding: Monte-Carlo study

A new kind of continuous-wave (CW) cold molecular beam, methyl cyanide (CH₃CN) beam, is generated by a bent electrostatic quadrupole guiding. The Stark shift of rotational energy levels of CH₃CN molecule and its population distribution are calculated, and the dynamic processes of electrostatic guiding and energy filtering of CH₃CN molecules from a gas source with room temperature (300 K) are simulated by Monte Carlo Method. The study showed that the longitudinal and transversal temperatures of output cold CH₃CN beam could be about ∼ 2 K and ∼ 420 mK, and the corresponding guiding efficiency was about 10^-5 as the guiding voltage was 3 kV. Furthermore, the temperature of the guided molecules and its guiding efficiency can be controlled by adjusting the guiding voltages applied on electrodes.     

Spin dynamics in (( BEDO-TTF )6[ M (CN)6](H3O,CH3CN)2 ( M = Fe, Cr) crystals

Layered single crystals of the (BEDO-TTF)₆[M(CN)₆](H₃O,CH₃CN)₂ (M = Fe, Cr) compounds with alternating conducting layers of BEDO-TTF and [M(CN)₆](H₃O,CH₃CN)₂ are studied. The contributions to the magnetic susceptibility from charge carriers in BEDO-TTF layers and from the subsystem of localized magnetic moments of iron (or chromium) transition metal complexes are separated for both compounds under investigation. It is revealed that the crystals with [Fe(CN))₆]³⁻ anions at a temperature of ∼80 K and the crystals with [Cr(CN))₆]³⁻ anions at ∼30 K undergo magnetic transitions which are accompanied by drastic changes in the parameters of the EPR lines associated with the BEDO-TTF layers and the subsystem of localized spins of transition metal complexes. It is established that the presence of the BEDO-TTF layers in the structure affects the magnetic properties of iron and chromium hexacyanide complexes. Original Russian Text ? R.B. Morgunov, E.V. Kurganova, T.G. Prokhorova, E.B. Yagubskiĭ, S.V. Simonov, R.P. Shibaeva, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 4, pp. 657–663.     

Reactions and anion desorption induced by low-energy electron exposure of condensed acetonitrile

Thermal desorption spectrometry (TDS) and electron stimulated desorption (ESD) are employed to investigate mechanisms responsible for the formation of C₂H₆ in electron irradiated multilayer films of acetonitrile (CH₃CN) at 30 K. Using a high sensitivity time-of-flight mass spectrometer, we observe the ESD of anionic fragments H⁻, CH₂ ⁻, CH₃ ⁻ and CN⁻. Desorption occurs following dissociative electron attachment (DEA) via several negative ion resonances in the 6 to 14 eV energy range and correlates well with a “resonant” structure seen in the TDS yield of C₂H₆ (i.e., at mass 30 amu). It is proposed that C₂H₆ is formed by the reactions of CH₃ radicals generated following DEA to CH₃CN which also yields CN⁻. Between 2 and 5 eV, a second resonant feature is seen in the C₂H₆ signal. While DEA is observed in the gas phase at these energies, no anion desorption occurs since anionic fragments likely have insufficient kinetic energy to desorb. Since the CH₂ ⁻ ion has not been observed in gas-phase measurements, we propose that it is formed, along with HCN (that is detected in TDS) when dissociation into CH₃ ⁻ and CN is hindered by adjacent molecules.     

Radiative cooling of fullerene anions in a storage ring

Thermionic emission from hot fullerene anions, C_N ^-, has been measured in an electrostatic storage ring for even N values from 36 to 96. The decay is quenched by radiative cooling and hence the observations give information on the intensity of thermal radiation from fullerenes. The experiments are analysed by comparison with a simulation which includes the quantisation of photon energy and the statistics of emission. Experiments with heating of the molecules with a laser beam confirm the interpretation of the observations in terms of radiative cooling and give an independent estimate of the cooling rate for C₆₀ ^-. The measured cooling rates agree in general within a factor of two with the prediction from a classical dielectric model of a thermal radiation intensity of ∼ 300 eV/s for C₆₀ at 1 400 K, scaling approximately with the 6th power of the temperature and with the number of atoms in the molecule. Received 12 March 2001 and Received in final form 12 June 2001     

Frequency measurements in the b <Superscript>3</Superscript>Π(0<Subscript>u</Subscript><Superscript>+</Superscript>) - X <Superscript>1</Superscript>Σ<Subscript>g</Subscript><Superscript>+</Superscript> system of K<Subscript>2</Subscript>

Absolute transition frequencies of the b ³Π(0_u ⁺) - X ¹Σ_g ⁺ system of K₂ were measured in a molecular beam with Lamb dip absorption spectroscopy applying a frequency comb from a femtosecond pulsed laser. Both, K atoms and K₂ molecules are present in the beam and are expected to interact by collisions. The atoms can be deflected optically out of the beam, and thus the collision rate between K atoms and K₂ molecules is changed by about an order of magnitude. The molecular transition frequencies for low collisional rate are compared with those for high one. Limits for the collisional frequency shift within the beam are determined.     

Critical evolution of the local order parameters related to the nanopolar domains in Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> ceramics

In the present paper, Pb(Mg_1/3Nb_2/3)O₃ (PMN) ceramics prepared by the columbite method were investigated. The dielectric study indicates typical relaxor properties, with a frequency dispersion in the range of 200–350 K. The relaxor-to-paraelectric phase transition was evidenced by the continuous decrease of the local order parameter derived from the permittivity-temperature data. As a result of the critical behavior, the main Raman modes show anomalies at: (i) ∼150 K; (ii) ∼220 K (i.e. close to the critical temperature reported for the field-induced ferroelectric state in PMN single crystal); (iii) ∼260 K (i.e. the temperature of the permittivity maximum); (iv) ∼350 K (the temperature for initiation of the cluster freezing process T ^*); (v) ∼620 K (Burns temperature). The frequency split of the doublet at ∼605 and ∼500 cm⁻¹ presents a critical behavior related to the local symmetry lowering and to the structure ordering due to a phase transformation which takes place below T ^*. The tunability in the paraelectric state was interpreted in terms of reorientation of the non-interacting nanopolar clusters in a double-well potential. The temperature dependence of the nanopolar domain size also shows anomalies in the range of T ^*. The size and dynamics of the polar nanodomains is essential in determining the functional properties of the Pb(Mg_1/3Nb_2/3)O₃ relaxor.     

Study of opto-mechanical characteristics of interaction of ultrashort laser pulses with polymer materials

The opto-mechanical characteristics, such as the specific mechanical recoil momentum, the specific impulse, and the energy efficiency, of the laser ablation of flat polymer targets ((C₂F₄) _n , (CH₂O) _n ) have been determined experimentally for the first time for the case of excitation with femtosecond pulses (τ ∼ 45–70 fs) of UV-IR (λ ∼ 266, 400, 800 nm) laser radiation (I ₀ up to 10¹⁵ W/cm²) under normal atmospheric and vacuum (p ∼ 10⁻⁴ mbar) conditions. The efficiency of mechanical recoil momentum generation is analyzed for various regimes of the laser irradiation.     

Hyperfine interactions in molecules through laser spectroscopy

The infrared and millimeter wave spectroscopy, laser Stark spectroscopy, and beam maser spectroscopy of CH₃CN and its isotopic species will be discussed. The beam maser spectroscopy and hyperfine structure of molecules like NCCCD, ClCCD and CH₃CCH are reviewed. The laser magnetic resonance and hyperfine structure in CF, CH and CH₂ free radicals will be discussed. The Lamb dip spectroscopy and laser-induced fluorescence in I₂ involving theB ³Π(0 _u ⁺ ) state are reviewed with special reference to its hyperfine structure. The splitting of the rotational levels of N ₂ ⁺ in itsX ²Σ _g ⁺ andB ²Σ _u ⁺ states due to hyperfine interactions (along with the hyperfine structure) in laser-induced fluorescence in theB−X transition is discussed. Recent results obtained in the laser photo-acoustic spectrum of ICl in the transitionX ¹Σ⁺ −A ³Π₁ will be presented and the possibility of the use of this technique in studying the hyperfine structure will be discussed.     

Decomposition of nitromethane in shock waves: The primary stage and the kinetics of decomposition at pressures of about 40 atm

The kinetics of nitromethane (NM) decomposition and the observed rate constant of the process were measured behind reflected shock wave using absorption spectroscopy at λ = 230 nm, temperatures of 1060 to 1350 K, pressure of ∼40 atm, and initial reactant concentration within 30–100 ppm. It was observed that, at the initial stage, nitromethane decomposes exponentially, without autoacceleration. The results of numerical simulations with the help of three most known kinetic schemes of nitromethane decomposition proved to be in close to agreement with our experimental data over the entire temperature range covered. It was demonstrated that the measured rate constant is identical to the rate constant of the dissociation CH₃NO₂ → CH₃ + NO₂. The temperature dependence of k ₁ was approximated by the Arrhenius formula k ₁ = 2.57 × 10¹⁴ exp(−52.85/RT) s⁻¹ (activation energy in kcal/mol), which suggests that the nitromethane dissociation proceeds in the falloff pressure region.     

The adsorption and reaction of Acetonitrile on clean and oxygen covered Ag(110) surfaces

The adsorption and reaction of acetonitrile (CH₃CN) on clean and oxygen covered Ag(110) surfaces has been studied using temperature programmed reaction spectroscopy (TPRS), isotope exchange, chemical displacement reactions and high resolution electron energy loss spectroscopy (EELS). On the clean Ag(110) surface, CH₃CN was reversibly adsorbed, desorbing with an activation energy of 10 kcal mol^-1 at 166 K from a monolayer state and at 158 K from a multilayer state. Vibrational spectra of multilayer, monolayer and sub-monolayer CH₃CN were in excellent agreement with that of gas phase CH₃CN indicating that CH₃CN is only weakly bonded to the clean Ag(110) surface. On the partially oxidized surface CH₃CN reacts with atomic oxygen to form adsorbed CH₂CN, OH and H₂O in addition to forming another molecular adsorption state with a desorption peak at 240 K. This molecular state shows a CN stretching frequency of 1840 cm^-1, which is indicative of substantial rehybridization of the CN bond and is associated with side-on coordination via the π system. The CH₂CN species is stable up to 430 K, where C-H bond breaking and reformation begins, leading to the formation of CH₃CN at 480 K and HCN at 510 K and leaving only carbon on the surface. In the presence of excess oxygen atoms C-H bond breaking and reformation is more facile leading to additional desorption peaks for CH₃CN and H₂O at 420 K. This destabilizing effect of O_(a) on Ch₂CN_(a) is explained in terms of an anionic (CH₂CN^-1) species. Comparison of the vibrational spectra from CH₂CN_(a) and CD₂CN_(a) supports the following assignment for the modes of adsorbed CH₂CN: ν(Ag-C) 215: δ(CCN) 545; ϱ_t(CH₂) 695; ϱ_w(CH₂) 850; ν(C-C) 960; ϱ_r(CH₂) 1060; δ(CH₂) 1375; ν(CN) 2075; and ν(CH₂) 2940 cm^-1. These results serve to further indicate the wide applicability of the acid-base reaction concept for reactions between gas phase Brönsted acids and adsorbed oxygen atoms on solver surfaces.     

A controllable double-well optical trap for cold atoms (or molecules) using a binary <Emphasis Type="Italic">π</Emphasis>-phase plate: experimental demonstration and Monte Carlo simulation

We experimentally demonstrate a practical scheme to form a controllable double-well optical dipole trap for cold atoms (or cold molecules), and give some experimental results as well as the fabrication method of a binary π-phase plate. The dependence of the double-well characteristics on the phase etching error of the π-phase plate and the evolution of the double-well optical trap from two wells to a single one are studied both theoretically and experimentally, and the experimental results are consistent with the theoretical prediction. Furthermore, the dynamic process of loading and splitting of cold ⁸⁷Rb atoms from a standard magneto-optical trap (MOT) into our controllable double-well one are studied by Monte Carlo simulations. Our study shows that the loading efficiency of cold atoms from the standard MOT into our single-well trap can reach 100%, and the relative atomic density will be reduced from 1.0 to ∼0.5 during the evolution of our double-well trap, in which the temperature of cold atoms is reduced from 20 μK to ∼15 μK. In final, some potential applications of our controllable double-well optical trap in atom and molecule optics are briefly discussed.     

Chemical dynamics of muonium in liquids

The bimolecular rate constants for muonium addition to ethene (CH₂=CH₂) in hydrocarbon liquids were found to be ∼2×10¹⁰ M⁻¹s⁻¹. These rate constants change with temperature in accordance with the Arrhenius equation; but the energy barrier to reaction (E_a) in 2-methylbutane is much less than that for viscous flow. This suggests either non-classical interaction rates stemming from the quantum character for muonium, or non-Stokes-Einstein behavior.     

Experimental study of optical gas-dynamic processes of polymeric material ablation by ultrashort laser pulses

Optical gas-dynamic processes occurring in polymeric targets ((CH₂O) _n , (C₂F₄) _n ) exposed to ultrashort laser pulses (τ _0.5 ∼ 45 − 70 fs; λ _I,II,III = 266, 400, 800 nm; and E/S ∼ 0.1 − 40 J/cm² at r ₀ ∼ 20 μm) were studied under normal conditions and in vacuum (p ∼ 10⁻² Pa). The dynamics of the mass flow from the target surface (m′ ∼ 10⁻⁵ − 10⁻⁴ g/J) was studied and the spectral-energy thresholds of laser ablation, the electron density distribution (n _e ∼ 10¹⁴ − 10¹⁸ cm⁻³), the mass-averaged velocity of the material flow from the target surface (∼ 10³ m/s), and the chemical composition and average temperature in the near-surface plasma formation (T ∼ 5000 K) were determined using interference microscopy, emission spectroscopy, and shadowgraphy.     

Numerical study of the directed polymer in a 1 + 3 dimensional random medium

The directed polymer in a 1+3 dimensional random medium is known to present a disorder-induced phase transition. For a polymer of length L, the high temperature phase is characterized by a diffusive behavior for the end-point displacement R² ∼L and by free-energy fluctuations of order ΔF(L) ∼O(1). The low-temperature phase is characterized by an anomalous wandering exponent R²/L ∼L^ω and by free-energy fluctuations of order ΔF(L) ∼L^ω where ω∼0.18. In this paper, we first study the scaling behavior of various properties to localize the critical temperature T_c. Our results concerning R²/L and ΔF(L) point towards 0.76 < T_c ≤T₂=0.79, so our conclusion is that T_c is equal or very close to the upper bound T₂ derived by Derrida and coworkers (T₂ corresponds to the temperature above which the ratio remains finite as L ↦ ∞). We then present histograms for the free-energy, energy and entropy over disorder samples. For T ≫T_c, the free-energy distribution is found to be Gaussian. For T ≪T_c, the free-energy distribution coincides with the ground state energy distribution, in agreement with the zero-temperature fixed point picture. Moreover the entropy fluctuations are of order ΔS ∼L^1/2 and follow a Gaussian distribution, in agreement with the droplet predictions, where the free-energy term ΔF ∼L^ω is a near cancellation of energy and entropy contributions of order L^1/2.     

Force field calculations of acetonitrile using CNDO/force method

The redundancy-free internal valence force field (RFIVFF) of acetonitrile is reported using CNDO/force method. The initial force field is set up by taking the interaction and bending force constants from CNDO force field and transferring stretching force constants from the force fields of chemically related molecules. The final force field is obtained by refining the initial force field using vibrational harmonic frequencies of CH₃CN,¹³CH₃CN, CH₃ ¹³CN, CH₃C¹⁵N, CD₃CN and CD₃ ¹³CN. The final force field thus obtained is found to be excellent on the basis of frequency fit and potential energy distribution.     

The origin of disorder in CH 3 HgX (X = Cl, Br and I) crystals investigated by temperature dependent Raman spectroscopy

Methyl-mercury(II) halides CH₃HgX (X = Cl, Br and I) were studied by means of temperature dependent Raman spectroscopy from 10 K to 410 K. In addition to the previously reported soft phonons, new changes in the low frequency spectra were observed at T ≈ 70 K in CH₃HgBr and at T ≈ 100 K in CH₃HgI. The bandwidths of the two internal modes in CH₃HgBr, the CH₃ symmetric stretching band and the C-Hg-Br bending band, rise towards a local maximum at T ≈ 50 K as the temperature is raised from 10 K to 300 K. On the other hand the bandwidths of the two corresponding modes in CH₃HgI crystals monotonously increase with temperature, obeying an Arrhenius law. Besides the three phonon modes present in the Raman spectra of CH₃HgCl at room temperature, the fourth phonon band that has been observed at temperatures below 245 K might correspond to the freezing of methyl librations. The huge bandwidth of the C-Hg-Br bending mode could suggest the presence of additional weak bonding of a mercury atom with bromine atoms from other molecules, thus inducing positional disorder. Received 19 November 1999 and Received in final form 10 November 2000     

Efficiency of an electron-beam-pumped chemical laser with an SF6-H2 working mixture

Results are presented from a study of HF lasers pumped by non-chain chemical reactions initiated by a radially convergent and by a planar electron beam. The main channels of formation of vibrationally excited HF molecules are analyzed. The distribution of the energy density of the radiation in the output beam of a wide-aperture laser is measured. In 30 liters of a mixture of SF₆:H₂=8:1 at a pressure of 1.1 atm an output energy of ∼200 J is obtained at an ∼11% efficiency with respect to the energy deposition. It is shown that the admixture of a buffer gas of neon or argon improves the uniformity of the radiation energy distribution in the output beam of an HF laser pumped by a non-chain chemical reaction and initiated by an electron beam, and it also increases the output energy. Zh. Tekh. Fiz. 69, 76–81 (January 1999)     

Transverse beam asymmetries measured from <Superscript>4</Superscript>He and hydrogen targets

The HAPPEX Collaboration at Jefferson Lab has measured the transverse beam spin asymmetries (A_T) for elastic electron scattering from proton and ⁴He targets. The experiment was conducted using a vertically polarized electron beam of energy ∼ 3 GeV, at a Q ² ∼ 0.1 GeV^2 and a scattering angle θ_lab ∼ 6^° . The preliminary results are reported here. The ⁴He measurement is the first measurement of A_T from a nucleus. A_T for ⁴He is non-negligible; therefore, it will be necessary to make measurements of A_T for future parity-violating experiments using nuclear targets.     

Level structure of 99Rh at high spins

High spins states in ⁹⁹Rh were populated via the ⁶⁶Zn(³⁷Cl, 2p2n)⁹⁹Rh reaction at an incident beam energy of 130 MeV. Seventeen new transitions have been observed in the present study and the level scheme has now been extended up to a spin of J∼ 25ħ and an excitation energy of about E _x∼ 10 MeV. The observation of a positive parity E2 cascade based on the 9/2⁺ isomeric level is suggestive of collective behaviour in this nucleus up to high spins. Spherical shell model (within restricted model space) and Cranked shell model calculations were performed to obtain an insight into the observed level structure. The new collective band observed up to a spin of J∼ 25ħ is suggested to be based on (πg _9/2 ³) ⊗ (νg _7/2 ²) quasi-particle excitations. Received: 12 July 1999 / Revised version: 14 September 1999