We demonstrate rotational excitation of molecular ions that are sympathetically cooled by laser-cooled atomic ions to a temperature as low as approximately 10 mK. The molecular hydrogen ions HD${}^{+}$ and the fundamental rotational transition $(v=0,\phantom{\rule{0.16em}{0ex}}N=0)\ensuremath{\rightarrow}({v}^{\ensuremath{'}}=0,\phantom{\rule{0.16em}{0ex}}{N}^{\ensuremath{'}}=1)$ at 1.3 THz, the most fundamental dipole-allowed rotational transition of any molecule, are used as a test case. This transition has not been observed before. 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.
We demonstrate rotational excitation of molecular ions that are sympathetically cooled by laser-cooled atomic ions to a temperature as low as approximately 10 mK. The molecular hydrogen ions HD+ and the fundamental rotational transition (v=0,N=0)\ensuremath→(v\ensuremath′=0,N\ensuremath′=1) at 1.3 THz, the most fundamental dipole-allowed rotational transition of any molecule, are used as a test case. This transition has not been observed before. 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.
Hydrogen molecular ions play an important role for accurate quantum electrodynamics calculations of rovibrational energy levels [1] and the comparison with laser spectroscopy results [2] allowed probing fundamental physics constants and laws. Advances are driven by an accurate control of the external and internal molecular degrees of freedom with a wide range of techniques [3]. Experimental setups with HD+ions are based on ions in a linear Paul trap and sympathetically cooled to the Lamb-Dick confinement regime by a laser-cooled atomic ion (Be+). Optical transitions allowed rotational cooling [4] and state-resolved detection by resonant-enhanced-multiphoton dissociation (REMPD) [5]. This contribution reports numerical results on the use of a two-photon rotational transition in the terahertz frequency range for preparation of trapped HD+ions in the rovibrational ground state and for high-resolution spectroscopy.
Working with MgH+molecular ions in a linear Paul trap, we routinely cool their translational degrees of freedom by sympathetic cooling with Doppler laser cooled Mg+ions. Giving the time for the molecules to equilibrate internally to room temperature blackbody radiation, the vibrational degree of freedom is frozen out, leaving only the rotational degree of freedom to be cooled. We have implemented a new technique for laser-induced rotational ground-state cooling of vibrationally and translationally cold MgH+ions, using a scheme based on excitation of a single rovibrational transition. This technique is generalizable to any diatomic polar molecular ion, given an appropriate mid-infrared laser source such as a quantum cascade laser.
Sympathetic cooling of molecular ions through the Coulomb interaction with laser-cooled atomic ions is an efficient tool to prepare translationally cold molecules without, ideally, affecting the internal state of the molecular ions. However, the electric field due to the Coulomb interaction may induce rotational transitions that change the purity of initially quantum state prepared molecules. Here, we use estimates of rotational state changes in single collisions of diatomic ions with atomic ions [J. M. Berglund, M. Drewsen, and C. P. Koch, ] to determine the overall rotational excitation accumulated over the sympathetic cooling. Considering two different experimental scenarios, that of a molecular ion cotrapped with a single atomic ion and a molecular ion immersed in a Coulomb crystal of atomic ions, we also estimate the cooling time.
Sympathetic cooling of molecular ions through the Coulomb interaction with laser-cooled atomic ions is an efficient tool to prepare translationally cold molecules without, ideally, affecting the internal state of the molecular ions. However, the electric field due to the Coulomb interaction may induce rotational transitions that change the purity of initially quantum state prepared molecules. Here, we use estimates of rotational state changes in single collisions of diatomic ions with atomic ions [J. M. Berglund, M. Drewsen, and C. P. Koch, Phys. Rev. A 113, 042816 (2026)] to determine the overall rotational excitation accumulated over the sympathetic cooling. Considering two different experimental scenarios, that of a molecular ion cotrapped with a single atomic ion and a molecular ion immersed in a Coulomb crystal of atomic ions, we also estimate the cooling time.
We have measured the ro-vibrational infrared transition (v = 0, J = 2) → (v = 4, J = 1) in ultracold HD+ molecular ions embedded inside Be+ Coulomb crystals, by 1+1 REMPI spectroscopy. The molecular ions, trapped in a linear radiofrequency trap, were cooled to temperatures of few tens of mK, via sympathetic cooling using laser-cooled Be+ ions. For detection, we have used secular excitation of the HD+ ions to monitor their loss rate. The transition frequency agrees with a theoretical prediction.
In recent years there has been much progress in the field of cold and ultracold molecular physics and a variety of experimental techniques for producing cold matter now exist. In particular, the generation of trapped molecular ions at mK temperatures has been achieved by sympathetic-cooling with laser-cooled atomic ions. By implementing schemes to selectively prepare and control the internal quantum state of molecular ions, and developing detection techniques, it will be increasingly possible to study cold state-selected chemical collisions in an ion-trap. Most molecular species produced in a selected rovibrational state have a lifetime of a few seconds, before the population is redistributed across numerous rovibrational states by interaction with the ambient blackbody radiation (BBR). Consequently, the investigation of state-selected reaction dynamics at low temperatures in experiments where long time scales (minutes to hours) are required, is hindered. This thesis looks into developing strategies that maintain state selection in molecular ions, allowing one to observe state-selected reactions in cold environments, in particular the state-selected reaction between C2H+2 and ND3. Examining reactive ion molecule collisions under cold conditions provides insight into fundamental reaction dynamics, which are thermally averaged out at higher temperatures. A theoretical model is used to investigate laser-driven, blackbody-mediated, rotational cooling schemes for several 1Σ and 2Π diatomic species. The rotational cooling is particularly effective for DCl+ and HCl+, for which 92% and >99% (respectively) of the population can be driven into the rovibrational ground state. For the other systems a broadband optical pumping source is found to enhance the population that can be accumulated in the rovibrational ground state by up to 29% more than that achieved when exciting a single transition. The influence of the rotational constant, dipole moments and electronic state of the diatomics on the achievable rotational cooling is also studied. This approach is extended to consider the BBR interaction and rotational cooling of a linear polyatomic ion, C2H+2, which has a 2Π electronic ground state. The (1-0) band of the ν5 cis-bending mode is infrared active and strongly overlaps the 300 K blackbody spectrum. Hence the lifetimes of state-selected rotational levels are found to be short compared to the typical timescale of ion trapping experiments. Laser cooling schemes are proposed that could be experimentally viable, which involves simultaneous pumping of a set of closely spaced Q-branch transitions on the 2Δ5/2-2Π3/2 band together with two 2Σ+– 2Π1/2 lines. It is shown that this should lead to >70% of total population in the lowest rotational level at 300 K and over 99% at 77 K. In order to identify states of the acetylene ion that could be trapped sufficiently long enough for state-selected reactions in the ion trap with decelerated ND3, the theoretical work has been complemented by experimental investigations into the production of C2H+2 in selected states, and ion trapping of the same using sinusoidal and digital trapping voltages. Appropriate (2+1) REMPI (Resonance Enhanced Multiphoton Ionization) schemes are used to produce C2H+2 in different quantum states, with (1+1) Resonance Enhanced Multiphoton Dissociation (REMPD) employed to detect the ion thus produced. The concept of digital ion trapping for ejection onto MCPs is introduced. A comprehensive comparison between sinusoidal and digital trapping fields has been performed with respect to trap depth and stability regions. Programs have been developed to calculate the stability regions for different ions under varying experimental conditions. The trap depth has been derived for both digital and sinusoidal trapping fields. It is observed that as τ increases, the trap depth of a digital trap increases. For τ = 0.293, the trap depth and stability diagram for both sinusoidal and digital trapping fields would be equivalent. The trap depth at which the sinusoidal trap operates experimentally in our research group is ˜1.36 eV. In contrast, the experimental parameters at which the digital trap operates generates a trap depth of 1.21 eV. Ca+ Coulomb crystals have been formed, stably trapped and stored for extended periods of time in both sinusoidally and digitally time-varying trapping fields. The sympathetic cooling of a diverse range of ions into Ca+ Coulomb crystals is demonstrated, again using both sinusoidal and digital trapping fields. Mass spectrometric detection of ionic reaction products using a novel ejection scheme has been developed, where ejection is achieved by switching off the trapping voltage and converting the quadrupole trap into an extractor-repeller pair by providing the ion trap electrodes with appropriate ejection pulses. This technique is developed using a digital trapping voltage rather than the sinusoidal trapping voltage, as ejection with sinusoidal trapping voltages is not clean (resonance circuitry used in the electronics induces ringing after switching off the trapping voltage). Coulomb crystals, both pure Ca+ and multi-component crystals, are ejected from the ion trap and the TOF trace obtained is recorded on an oscilloscope. When the integrated, base-line subtracted TOF peak is plotted against the number of ions in a Ca+ crystal and sympathetically-cooled Ca+ – CaF+ crystal, a linear relationship is obtained. This technique is found to be well mass-resolved, with the signal arising from CaOH+ (57 amu) and CaOD+ (58 amu) resolvable on the TOF trace. This technique would enable one to monitor a reaction in a Coulomb crystal where the reactant and product species are both either lighter or heavier than calcium, such as the reaction between C2H+2 and ND3, something which has not been previously possible. It is, also, potentially a very important technique for reactions with many product channels.