A goal of studies on ultracold chemical reactions is the formation of
ultracold molecules containing three or more atoms. Although the first
ultracold polyatomic molecules were formed recently; knowledge of the kinetics
of polyatomic molecular ions as reaction products remains limited. Thus, we
studied ion-atom reaction collisions in a continuous-wave (CW) laser
photoionization of cold atoms in an Rb-Rb+ hybrid trap. A series of
polyatomic molecular ions was produced, with precise changes in the atomic
number of one rubidium atom. Using resonant-excitation mass spectrometry, we
directly observed Rb3+​ and Rb4+​ molecular ions in time-of-flight mass
spectrum for the first time. The information of the quantum state of these
polyatomic molecular ions and the influence factors was obtained by measuring
their lifetimes. The approach is simple, robust, and suitable for all types of
laser-coolable elements. Our work paves the way for ultracold ion-atom chemical
reactions, introduces the concept of polyatomic molecular ion platforms, and
deepens the understanding of ion-atom reaction collisions. It has important
implications for astronomical sciences, ultracold neutral plasma, cluster
physics, and other disciplines.Comment: 6 figures and 1 supplemental figure