Cold ion-polar-molecule reactions studied with a combined Stark-velocity-filter-ion-trap apparatus

Abstract

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 ND3, H2CO, and CH3CN, were performed using time-of-flight (TOF) measurements. We confirmed the generation of slow ND 3, H2CO, and CH3CN 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 106 cm-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 10-5 s-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 N2H+ ions and velocity-selected CH3CN molecules at the average reaction energy of about 3 K. The measured reaction rate of 2.0(2)×10-3 s -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+N2H+ → CH3CNH ++N2 is consistent with the estimated values from the room temperature results and the trajectory-scaling formula of Su 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. © 2013 American Physical Society.