A detailed investigation of ion crystals produced by laser and sympathetic cooling in a linear RF trap has been conducted.\n\nThe laser cooling methods were examined and applied to the trapped ^24Mg^(positive) ions. The crystals produced by the laser cooling were studied, including the dependence on RF voltage, end cap DC voltage, laser power and laser frequency. By manipulating the different RF voltages and endcap DC voltages, the structure phase transition of the ion crystals was observed.\n\nIn addition, the sympathetic cooling of different ion species with the laser cooled 24Mg^(positive) was carried out. In this process, the mixed Mg^(positive) and He^(positive) crystals were created andidentified, and mixed Mg^(positive) and H2^(positive) crystals were produced. The effect of an unwanted chemical reaction of Mg^(positive) and H2 was observed and minimized. After sympathetic cooling of light ion species, the sympathetic cooling of heavy molecular ions such as fullerene ions was also carried out. The efficiencies and final temperature in both cases are very different. Theoretically to interpret the results, molecular dynamics simulations of the laser cooling and sympathetic cooling were implemented. And the simulations were compared with the experimental results.\n\nIn the process of carrying out this research, the optics were rebuilt to provide reliable UV sources for the photoionization and laser cooling of Mg ions. The imaging\nsystem was reconfigured to take the images of ion crystals. New elements were added tin the ion trap to improve the ability to manipulate ions.
A detailed investigation of ion crystals produced by laser and sympathetic cooling in a linear RF trap has been conducted.\n\nThe laser cooling methods were examined and applied to the trapped ^24Mg^(positive) ions. The crystals produced by the laser cooling were studied, including the dependence on RF voltage, end cap DC voltage, laser power and laser frequency. By manipulating the different RF voltages and endcap DC voltages, the structure phase transition of the ion crystals was observed.\n\nIn addition, the sympathetic cooling of different ion species with the laser cooled 24Mg^(positive) was carried out. In this process, the mixed Mg^(positive) and He^(positive) crystals were created andidentified, and mixed Mg^(positive) and H2^(positive) crystals were produced. The effect of an unwanted chemical reaction of Mg^(positive) and H2 was observed and minimized. After sympathetic cooling of light ion species, the sympathetic cooling of heavy molecular ions such as fullerene ions was also carried out. The efficiencies and final temperature in both cases are very different. Theoretically to interpret the results, molecular dynamics simulations of the laser cooling and sympathetic cooling were implemented. And the simulations were compared with the experimental results.\n\nIn the process of carrying out this research, the optics were rebuilt to provide reliable UV sources for the photoionization and laser cooling of Mg ions. The imaging\nsystem was reconfigured to take the images of ion crystals. New elements were added tin the ion trap to improve the ability to manipulate ions.
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=720a.u.) fullerene ions to under 10K by the means of the sympathetic cooling by the Mg+ ions(m=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.
Coulomb crystals, containing up to a few hundred ions of which more than 50% were cooled sympathetically by the Coulomb interaction with laser cooled Mg+ ions, have been produced in a linear Paul trap. By controlling the balance of the radiation pressure from the two cooling lasers, the Coulomb crystals could be segregated according to ion species. Previous studies of ion crystals and molecular dynamics simulations suggest that the temperature may be around 10 mK or lower. The obtained results indicate that a wide range of atomic and molecular ions, which due to their internal structures are not amenable to direct laser cooling, can be effectively cooled and localized (crystallized) in linear Paul traps. For high resolution spectroscopy of such ions this may turn out to be very useful.
A large sample $(N\ensuremath{\approx}{10}^{4})$ of fullerene ions (m=720a.u) is cooled by means of a much smaller number$(\ensuremath{\approx}100)$ of laser-cooled magnesium ions (m=24a.u). The results demonstrate that sympathetic cooling of large molecules to low temperatures is feasible. The temperature of the 24Mg+ ions in the mixed ${\mathrm{Mg}}^{+}\text{\ensuremath{-}}{{\mathrm{C}}_{60}}^{+}$ ion cloud stored in an rf trap is found to be TMg=5K from their fluorescence signal. Molecular dynamics simulations are used to obtain the corresponding equilibrium temperature of the fullerene ions, and show that TC60=14K.
This thesis reports on experimental and theoretical studies of the sympathetic cooling of complex molecular ions demonstrating that this general method for cooling atomic and molecular ions is reliable and efficient.
For this purpose, complex molecular ions and barium ions have been confined simultaneously in a linear Paul trap. The complex molecular ions are generated in an electrospray ionization system and transferred to the trap via a 2 m long octopole ion guide. These molecular ions are pre-cooled by room temperature helium buffer gas so that they can be captured by the trap. The atomic barium ions are loaded from a barium evaporator oven and are laser-cooled by a 493 nm cooling laser and a 650 nm repumping
laser. Due to the mutual Coulomb interaction among these charged particles, the kinetic energy of the complex molecular ions can be reduced significantly.
In our experiments we have demonstrated the sympathetic cooling of various molecules (CO2, Alexa Fluor 350, glycyrrhetinic acid, cytochrome c) covering a wide mass range from a few tens to 13000 amu. In every case the molecular ions could be cooled down to millikelvin temperatures.
Photo-chemical reactions of the 138Ba+ ions in the (2P1/2) excited state with gases such as O2, CO2, or N2O, could be observed. If the initial 138Ba+ ion ensemble is cold, the produced 138BaO+ ions are cold as well, with a similar temperature as the laser-cooled barium ions (a few tens of millikelvin). The back-reaction of 138BaO+ ions with neutral CO to 138Ba+ is possible and was observed in our experiments as well.
A powerful molecular dynamics (MD) simulation program has been developed. With this program dynamic properties of ion ensembles, such as sympathetic interactions or heating effects, have been investigated and experimental results have been analyzed to obtain, for example, ion numbers and temperatures. Additionally, the feasibility of nondestructive spectroscopy via an optical dipole excitation and the lineshape of rovibrational
transitions of 1.4 and 5.1 μm have been studied.
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.
In this work, the setup of an experiment aimed at high-precision laser spectroscopy of ultracold molecular hydrogen ions, started at the University of Konstanz in 1999 [1,2], was continued and first results were obtained. In particular, a new linear rf trap and a new trap supply electronics were built, the latter being capable of driving the linear rf trap with a maximum rf amplitude of > 1000V at a frequency of 14.2MHz. This made possible the simultaneous trapping of a large mass range (2u For laser cooling of Be+ ions, doubly resonant sum-frequency generation (DR-SFG) of 313nm laser light was performed between a resonantly frequency-doubled monolithic Nd:Yag laser and a Ti:sapphire laser, emitting at 532 and 760nm wavelength, respectively. An output power of P_UV > 100mW was achieved at 313nm wavelength, with a high spectral purity (rms short-term frequency fluctuations With this experimental setup, sympathetic cooling of N+, BeD+, BeH+, 4He+, HD+, and D+ ions by the laser-cooled Be+ ions was demonstrated, using laser-cooled fluorescence mass spectrometry (LCF-MS) to detect the sympathetically cooled species. Accordingly, sympathetic cooling at a minimum mass ratio of m(H2+)/m(Be+) = 0.22 was shown to be possible with both the sympathetically and laser-cooled ions in a cloud-like state. This points out the incorrectness of the theoretical lower limit m_SC/m_LC = 0.53 which was predicted in Ref.[3]. Here, the subscripts SC and LC denote the sympathetically and the laser-cooled species, respectively.
In a further experiment, almost pure Be+ ion plasmas were laser-cooled down to temperatures in the milli-Kelvin range, leading to the crystallization of the Be+ ion plasmas. The outer shapes of different-sized Be+ ion crystals in a fully anisotropic trap potential were compared with the charged fluid predictions, showing good agreement at sufficiently large numbers of Be+ ions. By fitting Voigt profiles to the measured fluorescence signal, a typical temperature T(Be+) of 30mK was estimated for the Be+ ions.
Finally, an ultracold sample of 4He+ ions [T(He+) approximately 40mK] was produced for the first time by sympathetic crystallization of the 4He+ ions. This may open up perspectives for the high-precision laser spectroscopy of 4He+ (and 3He+).
[1] T.K.W. Boley, Diplomarbeit, Universitat Konstanz (1999)
[2] H. Schnitzler, Dissertation, Universitat Konstanz (2001)
[3] T. Baba and I. Waki, Appl.Phys.B, 74, 375-382 (2002)