We have developed a combined Stark-velocity-filter--ion-trap apparatus for the purpose of reaction-rate measurements between cold trapped ions and slow polar molecules under ultrahigh vacuum conditions. The prerequisite steps such as the characterization of velocity-selected polar molecules (PM), namely ND
3, H
2CO, and CH
3CN, were performed using time-of-flight (TOF) measurements. We confirmed the generation of slow ND
3, H
2CO, and CH
3CN molecules having thermal energies of a few Kelvin. Additionally, the number densities of the slow velocity-filtered polar molecules were determined to be in the range of
n=104 to 10
6 cm${}^{\ensuremath{-}3}$ by calibrating the TOF signals. In a first experiment, the Stark velocity filter was connected to a cryogenic linear Paul trap and reaction-rate measurements between laser-cooled Ca
+ Coulomb crystals and velocity-selected polar molecules were carried out. The observed reaction rates are of the order of 10${}^{\ensuremath{-}5}$ s${}^{\ensuremath{-}1}$, which are much slower than typical reaction rates of molecular ion--polar-molecule reactions at low temperatures. The present results confirm that reaction-rate measurements between velocity-selected polar molecules and sympathetically cooled molecular ions cooled by a laser-cooled Ca
+ Coulomb crystal can be performed. Next we measured the reaction rates between sympathetically cooled nonfluorescent stored ion molecules namely N
2H
+ ions and velocity-selected CH
3CN molecules at the average reaction energy of about 3 K. The measured reaction rate of 2.0(2)$\ifmmode\times\else\texttimes\fi{}
10{}^{\ensuremath{-}3}$ s${}^{\ensuremath{-}1}$ is much faster than those of the Ca
++PM reactions. This is strong evidence that the velocity-selected polar molecules undergo reactive collisions. We also confirmed that the present reaction-rate constant of CH
3CN+N
2H
+ $\ensuremath{\rightarrow}$ CH
3CNH
++N
2 is consistent with the estimated values from the room temperature results and the trajectory-scaling formula of Su et al. In the future, the present velocity-filter combined cryogenic trap apparatus will enable us to perform systematic measurements of cold ion--polar-molecule reactions, which are important problems from a fundamental viewpoint and also contribute to astrochemistry.
Translationally cold and slow ND
3 is prepared by filtering the slow molecules from a thermal gas-phase sample using a curved electrostatic hexapole guide. This filter, like the curved quadrupole guide introduced by Rangwala et al. [Phys. Rev. A 67, 043406 (2003)] selects molecules by their forward velocity and effective electric dipole moment. Here we describe two main modifications with respect to previous work: (1) A segmented hexapole guide is used that produces a harmonic potential for the linearly Stark-shifted levels of ND
3. A curved guide is combined with a straight hexapole guide, and independent high-voltage supplies are employed to allow for bandpass velocity filtering. (2) State-selective laser ionization is used to obtain time- and state-selective detection of the guided molecules. This enables the experimental determination of the rotational state population of the guided molecules.
The interaction of polar molecules with an inhomogeneous, electrostatic field to filter molecules from an effusive room-temperature source is exploited to create a slow molecule beam. Whether a dipolar molecule is trapped in or expelled from the electric field minimum depends on the orientation of the molecular dipole with respect to the electric field. These molecules are called low and high-field seekers, respectively. Thus, an electric field configuration with a field minimum on axis acts as a 2-dimensional trap for low-field seeking molecules with small transverse velocity components. A linear quadrupolar is opted, which is one of the simplest suitable geometries. The longitudinal velocity is limited by a bent section, where the centripetal force due to the radius of curvature and electric field gradient guide only the slowest molecules around the bend.
We demonstrate experimentally the guiding of cold and slow ND
3 molecules along a thin charged wire over a distance of $\ensuremath{\sim}0.34$ m through an entire molecular beam apparatus. Trajectory simulations confirm that both linear and quadratic high-field-seeking Stark states can be efficiently guided from the beam source up to the detector. A density enhancement up to a factor 7 is reached for beams with velocities ranging down to $\ensuremath{\sim}150\phantom{\rule{0.28em}{0ex}}$m/s generated by the rotating nozzle technique.
This thesis describes the design and construction of a novel molecule-surface scattering apparatus. The setup combines a Stark decelerator with a state-of- the-art surface scattering chamber, and allows background-gas free scattering of packets of velocity-controlled polar molecules in selected quantum states from well-defined surfaces with unprecedented energy resolution. Results for scattering of CO (a3Π) in different vibrational quantum states from a clean Au(111) surface are presented. CO is co-expanded with Xe or Ar to yield a supersonic molecular beam which produces fast, internally cold molecules. Excitation of CO to the long-lived electronically excited a3Π1 state makes it accessible to manipulation with electric fields due to the state’s large dipole moment. The complete removal of both carrier gas and remaining ground- state CO is achieved by focusing and deflecting the metastable CO with a switched electrostatic hexapole state selector. The 131-stage Stark decelerator is used to tune the velocity of a part of the metastable CO pulse, with an initial velocity of 360 m/s, in the range from (512 ± 4) m/s – (50 ± 4) m/s, corresponding to an incident translational energy between (307 ± 5) cm-1 and (3.0 ± 0.5) cm-1, respectively.This range can be extended up to (1300 ± 25) m/s, corresponding to an energy of(1980 ± 80) cm-1, by simple modifications to the setup. Prior to collision, the molecules can be laser- prepared in different vibrational and rotational quantum states. State- selective detection of the scattering products makes it possible to determine the quantum state, the scattering angle, and the kinetic energy of the scattered molecules. Therefore, detailed information about the scattering process can be obtained. The design of the machine allows for flexible laser access near the surface, such that a variety of different preparation and detection schemes can be employed. Ultra-high vacuum conditions in the scattering chamber are achieved by baking the entire apparatus, including the decelerator and the hexapole. Because of the carrier gas removal and a total of three differential pumping stages, no pressure rise is detected in the scattering chamber due to the incident molecular beam. Scattering experiments of CO (a3Π) on Au(111) have been performed. The scattering process leads to electron emission because the metastable excitation energy exceeds the work function of the surface. The electron emission yield, i.e. the number of electrons emitted per incident metastable particle, has been measured to be 0.13 ± 0.05. A laser ionization-depletion method is used which makes it possible to directly compare the intensity of the metastable CO ionization signal to the intensity decrease of the electron emission signal. It was also shown that vibrationally excited metastable CO leads to a higher electron emission yield. By preparing different vibrational distributions of CO in the a3Π electronic state via Franck-Condon pumping, the electron emission yield was determined for groups of vibrational levels. The first three vibrationally excited levels have an increased electron emission yield which on average is a factor of 1.5 larger than that of the vibrational ground state. Averaged over the vibrational levels with quantum number v = 4, 5, 6 , this factor is approximately 2.6 . In the range between 93 m/s and 512 m/s, the electron emission was observed to be independent of the velocity of the incident molecules. When the surface temperature is raised from 250 K to 900 K, the intensity of the electron emission signal increases by 27 %. These results are not in agreement with the models currently used to describe the de-excitation of electronically excited molecules at metal surfaces. This demonstrates the need for more theoretical work to incorporate the role of vibration into the description of the de-excitation mechanism.