Alexander Petrov

We present experimental evidence of charge exchange between laser-cooled potassium $^{39}$K atoms and calcium $^{40}$Ca$^+$ ions in a hybrid atom-ion trap and give quantitative theoretical explanations for the observations. The $^{39}$K atoms and $^{40}$Ca$^+$ ions are held in a magneto-optical (MOT) and a linear Paul trap, respectively. Fluorescence detection and high resolution time of flight mass spectra for both species are used to determine the remaining number of $^{40}$Ca$^+$ ions, the increasing number of $^{39}$K$^+$ ions, and $^{39}$K number density as functions of time. Simultaneous trap operation is guaranteed by alternating periods of MOT and $^{40}$Ca$^+$ cooling lights, thus avoiding direct ionization of $^{39}$K by the $^{40}$Ca$^+$ cooling light. We show that the K-Ca$^+$ charge-exchange rate coefficient increases linearly from zero with $^{39}$K number density and, surprisingly, the fraction of $^{40}$Ca$^+$ ions in the 4p\,$^2$P$_{1/2}$ electronically-excited state. Combined with our theoretical analysis, we conclude that these data can only be explained by a process that starts with a potassium atom in its electronic ground state and a calcium ion in its excited 4p\,$^2$P$_{1/2}$ state producing ground-state $^{39}$K$^+$ ions and metastable, neutral Ca\,(3d4p$^3$P$_1$) atoms, releasing only 150 cm$^{-1}$ equivalent relative kinetic energy. Charge-exchange between either ground- or excited-state $^{39}$K and ground-state $^{40}$Ca$^+$ is negligibly small as no energetically-favorable product states are available. Our experimental and theoretical rate coefficients of $9\times10^{-10}$ cm$^3$/s are in agreement given the uncertainty budgets.

An important physical process unique to neutral-ion systems is the charge-transfer (CT) reaction. Here, we present measurements of and models for CT processes between co-trapped ultracold Ca atoms and Yb ions under well-controlled conditions. The theoretical analysis reveals the existence of three reaction mechanisms when lasers from a magneto-optical trap (MOT) and an additional catalyst laser are present. Besides the direct CT involving existent excited Ca population in the MOT, the second pathway is controlled by MOT-induced CT, whereas the third one mostly involves the additional red-detuned laser.

We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl$^+$. The photodissociation cross section for the photon energy range 35,500 cm$^{-1}$ to 47,500 cm$^{-1}$ is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43,000 cm$^{-1}$. The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl$^+$ is extremely complex due to the presence of multiple open electronic shells, including the 4f$^{10}$ configuration. The molecule has nine attractive potentials with ionically-bonded electrons and 99 repulsive potentials dissociating to a ground state Dy$^+$ ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.

The photodissociation cross-section of SrCl$^+$ is measured in the spectral range of 36000 -- 46000 cm$^{-1}$ using a modular time-of-flight mass spectrometer (TOF-MS). By irradiating a sample of trapped SrCl$^+$ molecular ions with a pulsed dye laser, X$^1Σ^+$ state molecular ions are electronically excited to the repulsive wall of the A$^1Π$ state, resulting in dissociation. Using the TOF-MS, the fragments are detected and the photodissociation cross-section is determined for a broad range of photon energies. Detailed $\textit{ab initio}$ calculations of the molecular potentials and spectroscopic constants are also performed and are found to be in good agreement with experiment. The spectroscopic constants for SrCl$^+$ are also compared to those of another alkaline earth chalcogen, BaCl$^+$, in order to highlight structural differences between the two molecular ions. This work represents the first spectroscopy and $\textit{ab initio}$ calculations of SrCl$^+$.

Interactions between cold ions and atoms have been proposed for use in implementing quantum gates\cite{Idziaszek2007}, probing quantum gases\cite{Sherkunov2009}, observing novel charge-transport dynamics\cite{Cote2000}, and sympathetically cooling atomic and molecular systems which cannot be laser cooled\cite{Smith2005,Hudson2009}. Furthermore, the chemistry between cold ions and atoms is foundational to issues in modern astrophysics, including the formation of stars, planets, and interstellar clouds\cite{Smith1992}, the diffuse interstellar bands\cite{Reddy2010}, and the post-recombination epoch of the early universe\cite{Stancil1996b}. However, as pointed out in refs 9 and 10, both experimental data and a theoretical description of the ion-atom interaction at low temperatures, reached in these modern atomic physics experiments and the interstellar environment, are still largely missing. Here we observe a chemical reaction between ultracold $^{174}$Yb$^+$ ions and $^{40}$Ca atoms held in a hybrid trap. We measure, and theoretically reproduce, a chemical reaction rate constant of $ \rm \bf K =(2\pm1.3)\times10^{-10} cm^{3}s^{-1}$ for $ \rm \bf 1 mK \leq T \leq 10 K$, four orders of magnitude higher than reported for other heteronuclear cases. We also offer a possible explanation for the apparent contradiction between typical theoretical predictions and measurements of the radiative association process in this and other systems.

We demonstrate a simple technique for molecular ion spectroscopy. BaCl$^+$ molecular ions are trapped in a linear Paul trap in the presence of a room-temperature He buffer gas and photodissociated by driving an electronic transition from the ground X$^1Σ^+$ state to the repulsive wall of the A$^1Π$ state. The photodissociation spectrum is recorded by monitoring the induced trap loss of BaCl$^+$ ions as a function of excitation wavelength. Accurate molecular potentials and spectroscopic constants are determined. Comparison of the theoretical photodissociation cross-sections with the measurement shows excellent agreement. This study represents the first spectroscopic data for BaCl$^+$ and an important step towards the production of ultracold ground-state molecular ions.