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Journal of Applied Physics

Spectral shape of in situ mass spectra of sympathetically cooled molecular ions

Takashi Baba, Izumi Waki

Published Sep 19, 2002• 26 citations
Publisher

Abstract

We formulated a model to reproduce the spectral shape of in situ mass spectra of sympathetically cooled molecular ions trapped in a linear radio-frequency-quadrupole. The molecular ions are sympathetically cooled by laser cooled ions. The mass spectrum is obtained by observing fluorescence emitted from the laser-cooled ions as we excite the resonant motion of the sympathetically cooled molecular ions in the trap. The model, which uses a pseudopotential and space-charge approach, reproduces the mass spectra of molecules. The model suggests that the variation of the space-charge density of the laser-cooled ions can produce in-trap kinetic excitation without the loss of the excited ions from the trap.

DOI
10.1063/1.1506005

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We formulated a model to reproduce the spectral shape of in situ mass spectra of sympathetically cooled molecular ions trapped in a linear radio-frequency-quadrupole. The molecular ions are sympathetically cooled by laser cooled ions. The mass spectrum is obtained by observing fluorescence emitted from the laser-cooled ions as we excite the resonant motion of the sympathetically cooled molecular ions in the trap. The model, which uses a pseudopotential and space-charge approach, reproduces the mass spectra of molecules. The model suggests that the variation of the space-charge density of the laser-cooled ions can produce in-trap kinetic excitation without the loss of the excited ions from the trap.
This paper presents the first sympathetic cooling of molecular ions using laser-cooled atomic ions. To this end, we developed a novel combination of sympathetic cooling and in situ mass spectroscopy that allows the use of laser-cooled atomic ions to detect sympathetically-cooled molecular ions non-destructively. We demonstrate this technique by cooling and mass-analysing ions of ultra-high-vacuum residual gas and externally introduced air in situ with less than 80 ions each, confined in a radio-frequency quadrupole (RFQ). This capability to detect and identify sympathetically-cooled molecules with potentially-high sensitivity in situ in an RFQ should be useful for molecular spectroscopy, chemical analysis and study of cold molecules and clusters.
Trapping molecular ions that have been sympathetically cooled with laser-cooled atomic ions is a useful platform for exploring cold ion chemistry. We designed and characterized a new experimental apparatus for probing chemical reaction dynamics between molecular cations and neutral radicals at temperatures below 1 K. The ions are trapped in a linear quadrupole radio-frequency trap and sympathetically cooled by co-trapped, laser-cooled, atomic ions. The ion trap is coupled to a time-of-flight mass spectrometer to readily identify product ion species and to accurately determine trapped ion numbers. We discuss, and present in detail, the design of this ion trap time-of-flight mass spectrometer and the electronics required for driving the trap and mass spectrometer. Furthermore, we measure the performance of this system, which yields mass resolutions of m/Δm ≥ 1100 over a wide mass range, and discuss its relevance for future measurements in chemical reaction kinetics and dynamics.
This work presents various novel results in the field of experimental and theoretical trapped ion studies. All investigations involve laser-cooled 138Ba+ ions confined in a linear quadrupole ion trap, which serve as coolant for complex molecular ions, as target for collisions with neutral atoms, or as model system in theoretical analyses. The special feature of the apparatus used in this work, is a molecular ion source based on electrospray ionization that allows for the production of gas-phase molecular ions of almost arbitrary species with a maximum mass-to-charge ratio of 2,000 Da. Trapped together with laser-cooled 138Ba+ ions, the molecular ions can be cooled down, kept cold and investigated for many minutes and in principle for up to hours in a nearly collisionless environment. In this work, the sympathetic cooling of complex molecular ions to translational temperatures below 1 K is demonstrated for different types of molecules covering a mass range from 182 to 12,400 Da. Using the example of the protein cytochrome c, with a mass of about 12,400 Da the most massive molecular species sympathetically cooled in an ion trap so far, the methods for detection of successful trapping and cooling, and temperature determination are presented in detail. In one case, multiply protonated molecules of the protein cytochrome c have been cooled to less than 0.75 K. Furthermore, two methods for measuring photodestruction rates of cold, trapped complex molecular ions have been developed that can, for example, be applied in destructive spectroscopy schemes. Both techniques are demonstrated using the example of singly protonated glycyrrhetinic acid molecules (GAH+) dissociated by an ultraviolet (UV) laser. Measurements of the photodestruction rate were performed at different intensities of the UV laser, and rates as low as 0.05 s-1 and less have been determined, which is only possible due to the long ion storage times that can be achieved with this apparatus. For the UV laser wavelength of 266 nm, a destruction cross section of (1.1±0.1)∙10E-17 cm2 for GAH+ has been determined. In this work, feasibility studies towards internal cooling of trapped complex molecular ions have been performed. Such an additional internal cooling could be realized via collisions with laser-cooled neutral atoms. To test their suitability, neutral atoms of Li, Na, K, Rb, Cs, and Yb have been collided with trapped laser-cooled and not cooled Ba+ ions as well as with complex molecular ions. For all species charge exchange reactions with Ba+ ions have been observed excluding these species for collisional cooling. While K, Rb, and Cs showed charge exchange reactions with ground state and laser-excited Ba+ ions, the charge exchange rates of Yb and Ba+ were found to be state dependent. Collisions of neutral Yb atoms were found to be reactive and lead to the formation of adducts and fragments, in contrast to the alkali metals for which no such reactions have been observed. In addition, the motion of cooled, trapped ions has been studied theoretically via simulations. When the translational energy of a trapped ion ensemble is sufficiently reduced, a first-order phase transition from a liquid to a solid state occurs with the ion ensemble changing from a disordered ion cloud to an ordered ion crystal. As ions in a linear quadrupole trap arrange in shell structures, a free motion in radial direction is disabled, and ions can only move to neighboring shells when their kinetic energy is high enough to overcome a certain potential barrier. The simulations have shown that intershell diffusion rates in the considered ion crystals increase exponentially when the ion temperatures exceed values that well agree with the predictions of other established models. Ion ensembles of different ion numbers (300, 500, and 1000 138Ba+ ions) and symmetries (prolate and spherical) have been investigated showing a clear tendency for the phase transition temperatures: The higher the ion number, the lower is the transition temperature.
An investigation of the sympathetic cooling \nmethod for the studies of large ultra-cold molecular ions in a quadrupole ion trap has been conducted.Molecular dynamics simulations are performed to study the rf heating mechanisms in the ion trap. The dependence of \nrf heating rates on the ion temperature, trapping parameters, \nand the number of ions is obtained. New rf heating mechanism \naffecting ultra-cold ion clouds exposed to laser radiation is described.The saturation spectroscopy setup of the hyperfine spectra \nof the molecular iodine has been built to provide an accurate frequency reference for the laser wavelength. This reference is used to obtain the fluorescence lineshapes of \nthe laser cooled Mg+^++ ions under different trapping conditions.The ion temperatures are deduced from the measurements, and \nthe influence of the rf heating rates on the fluorescence lineshapes \nis also discussed. Cooling of the heavy (m=720m=720m=720a.u.) fullerene ions to under 10K by the means of the sympathetic cooling by the Mg+^++ ions(m=24m=24m=24a.u.) is demonstrated. The single-photon imaging system has been developed and used to obtain the images of the Mg+^++ ion crystal structures at mK temperatures.