S. Schiller

Optical spectroscopy in the gas phase is a key tool to elucidate the structure of atoms and molecules and of their interaction with external fields. The line resolution is usually limited by a combination of first-order Doppler broadening due to particle thermal motion and of a short transit time through the excitation beam. For trapped particles, suitable laser cooling techniques can lead to strong confinement (Lamb-Dicke regime, LDR) and thus to optical spectroscopy free of these effects. For non-laser coolable spectroscopy ions, this has so far only been achieved when trapping one or two atomic ions, together with a single laser-coolable atomic ion [1,2]. Here we show that one-photon optical spectroscopy free of Doppler and transit broadening can also be obtained with more easily prepared ensembles of ions, if performed with mid-infrared radiation. We demonstrate the method on molecular ions. We trap approximately 100 molecular hydrogen ions (HD$^{+}$) within a Coulomb cluster of a few thousand laser-cooled atomic ions and perform laser spectroscopy of the fundamental vibrational transition. Transition frequencies were determined with lowest uncertainty of 3.3$\times$10$^{-12}$ fractionally. As an application, we determine the proton-electron mass ratio by matching a precise ab initio calculation with the measured vibrational frequency.

Advanced techniques for manipulation of internal states, standard in atomic physics, are demonstrated for a charged molecular species for the first time. We address individual hyperfine states of ro-vibrational levels of a diatomic ion by optical excitation of individual hyperfine transitions, and achieve controlled transfer of population into a selected hyperfine state. We use molecular hydrogen ions (HD^{+}) as a model system and employ a novel frequency-comb-based, continuous-wave 5 \mum laser spectrometer. The achieved spectral resolution is the highest obtained so far in the optical domain on a molecular ion species. As a consequence, we are also able to perform the most precise test yet of the ab-initio theory of a molecule.

We demonstrate rotational excitation of molecular ions that are sympathetically cooled by laser-cooled atomic ions to a temperature as low as ca. 10 mK. The molecular hydrogen ions HD+ and the fundamental rotational transition $(v=0,\, N=0)\rightarrow(v'=0,\, N'=1)$ at 1.3 THz, the most fundamental dipole-allowed rotational transition of any molecule, are used as a test case. This transition is here observed for the first time directly. Rotational laser cooling was employed in order to increase the signal, and resonance-enhanced multiphoton dissociation was used as detection method. The black-body-radiation-induced rotational excitation is also observed. The extension of the method to other molecular species is briefly discussed.

In this work we demonstrate vibrational spectroscopy of polyatomic ions that are trapped and sympathetically cooled by laser-cooled atomic ions. We use the protonated dipeptide tryptophane-alanine (HTyrAla+) as a model system, cooled by Barium ions to less than 800mK secular temperature. The spectroscopy is performed on the fundamental vibrational transition of a local vibrational mode at 2.74 μm using a continuous-wave optical parametric oscillator (OPO). Resonant multi-photon IR dissociation spectroscopy (without the use of a UV laser) generates charged molecular fragments, which are sympathetically cooled and trapped, and subsequently released from the trap and counted. We measured the cross section for R-IRMPD under conditions of low intensity, and found it to be approximately two orders smaller than the vibrational excitation cross section. The observed rotational bandwidth of the vibrational transition is larger than the one expected from the combined effects of 300 K black-body temperature, conformer-dependent line shifts, and intermolecular vibrational relaxation broadening (J. Stearns et al., J. Chem. Phys., 127, 154322-7 (2007)). This indicates that as the internal energy of the molecule grows, an increase of the rotational temperature of the molecular ions well above room temperature (up to on the order of 1000K), and/or an appreciable shift of the vibrational transition frequency (approx. 6-8 cm$^{-1}$) occurs.

In this work, we demonstrate measurements of photodestruction rates of translationally cold, charged biomolecules. The long-term stable storage of the molecular ions in an ion trap at ultra-high vacuum conditions allows measurement of small rates and verification that rates are linear in photodestruction laser intensity. Measurements were performed on singly protonated molecules of the organic compound glycyrrhetinic acid (C30H46O4), dissociated by a continuous-wave UV laser (266 nm) using different intensities. The molecules were sympathetically cooled by simultaneously trapped laser-cooled barium ions to translational temperatures of below 150 mK. Destruction rates of less than 0.05 s^-1 and a cross section of (1.1 +/- 0.1) * 10^-17 cm^2 have been determined. An extension to tunable UV laser sources would permit high-resolution dissociation spectroscopic studies on a wide variety of cold complex molecules.

Gas-phase multiply charged proteins have been sympathetically cooled to translational temperatures below 1 K by Coulomb interaction with laser-cooled barium ions in a linear ion trap. In one case, an ensemble of 53 cytochrome c molecules (mass ~ 12390 amu, charge +17 e) was cooled by ~ 160 laser-cooled barium ions to less than 0.75 K. Storage times of more than 20 minutes have been observed and could easily be extended to more than an hour. The technique is applicable to a wide variety of complex molecules.

We have generated Coulomb crystals of ultracold $^4$He$^+$ ions in a linear radiofrequency trap, by sympathetic cooling via laser--cooled $^9$Be$^+$. Stable crystals containing up to 150 localized He$^+$ ions at $\sim$20 mK were obtained. Ensembles or single ultracold He$^+$ ions open up interesting perspectives for performing precision tests of QED and measurements of nuclear radii. The present work also indicates the feasibility of cooling and crystallizing highly charged atomic ions using $^9$Be$^+$ as coolant.

It is shown that the translational degrees of freedom of a large variety of molecules, from light diatomic to heavy organic ones, can be cooled sympathetically and brought to rest (crystallized) in a linear Paul trap. The method relies on endowing the molecules with an appropriate positive charge, storage in a linear radiofrequency trap, and sympathetic cooling. Two well--known atomic coolant species, ${}^9{\hbox{Be}}^+$ and ${}^{137}{\hbox{Ba}}^+$, are sufficient for cooling the molecular mass range from 2 to 20,000 amu. The large molecular charge required for simultaneous trapping of heavy molecules and of the coolant ions can easily be produced using electrospray ionization. Crystallized molecular ions offer vast opportunities for novel studies.