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.      

Laser guiding of cold molecules in a hollow optical fiber and continuous-wave cold molecular beam generation

A novel scheme for guiding arbitrary buffer-gas cooled neutral molecules in a hollow optical fiber (HOF) using a red-detuned HE₁₁ mode is proposed and analysed theoretically. We give the electromagnetic field distribution of the HE₁₁ mode in the HOF and calculate the optical potential of an I₂ molecule, and study the molecule guiding mechanism using a classical Monte Carlo simulation. Using a 6 kW input laser, an S-shape HOF with a 2 cm curvature radius for both bends, and an input molecular beam with a transverse temperature of 0.5 K and longitudinal temperature of 5 K, we obtain a guiding efficiency of ～0.126% for the scheme, and the transverse and longitudinal temperatures of the guided molecular beam are 1.9 mK and 0.5 K, respectively.     

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.     

Electrostatic surface guiding for cold polar molecules: experimental demonstration

We demonstrate an electrostatic surface guiding for cold polar molecules over a long distance of 44.5 cm, 0.85 mm above a dielectric substrate, and measure the transverse distribution of the guided supersonic D2O/CH3Br beam and its longitudinal velocity one. Also, we study the dependence of the relative guiding efficiency and the transverse temperature of the guided molecular beam on the guiding voltage, and show that the absolute guiding efficiencies from the Monte Carlo simulation and theoretical calculation multiplied by 3 are about equal to the measured relative one.     

Generation of intense pulsed low-kinetic-energy molecular beams

A method for the generation of intense pulsed low-kinetic-energy molecular beams is described. The method is based on the formation of a cold (≈77 K) pressure shock as a result of interaction between an intense pulsed gas-dynamically cooled molecular beam with a solid surface. The pressure shock is used as a source of a secondary beam for generating low-energy molecules. The suggested method was used to obtain intense molecular beams of H₂, He, CH₄, N₂, and Kr with kinetic energies lower than or equal to 10 meV and H₂/Kr and He/Kr molecular beams with kinetic energies of H₂ and He molecules lower than 1 meV. The energy (velocity) of molecules in low-energy beams can be controlled by varying the intensity of the initial beam or temperature in the pressure shock.     

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.     

Production of cold CN molecules by photodissociating ICN precursors in brute-force field

We theoretically investigate the production of cold CN molecules by photodissociating ICN precursors in a brute-force field. The energy shifts and adiabatic orientation of the rotational ICN precursors are first investigated as a function of the external field strength. The dynamical photofragmentation of ICN precursors is numerically simulated for cases with and without orienting field. The CN products are compared in terms of their velocity distributions. A small portion of the CN fragments are recoiled to near zero speed in the lab frame by appropriately selecting the photo energy for dissociation. With a precursor ICN molecular beam of ～ 1.5 K in rotational temperature, the production of low speed CN fragments can be improved by more than 5 times when an orienting electrical field of 100 k V/cm is present. The corresponding production rate for decelerated fragments with speeds ≤ 50 m/s is simulated to be about ～2.1×10~(-4) and CN number densities of 10~(8) –10~(10) cm~(-3) can be reached with precursor ICN densities of ～10~(12) –10~(14) cm~(-3) from supersonic expansion.     

A versatile electrostatic trap with open optical access

A versatile electrostatic trap with open optical access for cold polar molecules in weak-field-seeking state is proposed in this paper. The trap is composed of a pair of disk electrodes and a hexapole. With the help of a finite element software, the spatial distribution of the electrostatic field is calculated. The results indicate that a three-dimensional closed electrostatic trap is formed. Taking ND₃ molecules as an example, the dynamic process of loading and trapping is simulated. The results show that when the velocity of the molecular beam is 10 m/s and the loading time is 0.9964 ms, the maximum loading efficiency reaches 94.25% and the temperature of the trapped molecules reaches about 30.3 mK. A single well can be split into two wells, which is of significant importance to the precision measurement and interference of matter waves. This scheme, in addition, can be further miniaturized to construct one-dimensional, two-dimensional, and three-dimensional spatial electrostatic lattices.     

Methyl cianide: Spectroscopic studies of isotopically substituted species,and the harmonic potential function

The infrared gas-phase spectra of CH₃CN, ¹³CH₃CN, CH₃¹³CN, CH₃C¹⁵N, CD₃CN, and CD₃¹³CN have been studied in detail, in order to determine accurately the fundamental vibration frequency displacements on heavy isotopic substitution. A number of important Fermi resonances have been identified, and treated quantitatively. The unperturbed fundamental frequencies and heavy isotopic displacements form a self-consistent set of data, which, together with Coriolis zeta and centrifugal distortion constants, enable the harmonic potential function of methyl cyanide to be determined with only one constraint. A comparison between the latter and results from an ab initio calculation reveals disagreement in the values of two interaction constants, which seem well outside our experimental error. Infrared frequencies in crystalline films of CD₃CN and CD₃¹³CN at 78 K are also reported.     

Quantum-mechanical high temperature Equation of state: Perturbation theory with finite range Kac potential

Angular distribution measurements of reactive scattering of a supersonic potassium atom beam by a series of halogen and halomethane molecules are reported with initial kinetic energies E ～ 5–6 kcal mol^-1. Differential reaction cross sections for I₂, IBr, CH₂I₂ show decreased wide-angle scattering and decreased total reaction cross sections compared with thermal energies. The differential reaction cross section for CHI₃ is peaked in the forward direction (?=0°) but that for CBr₄ peaks sideways at ? ～ 40°. The variation in reaction dynamics is correlated with the potential energy curves of halomethane molecules and their anions as indicated by dissociative thermal electron attachment experiments.