Laser cooling of CaF molecules

Cold and ultracold molecules are highly desirable for a diverse range of applications in physics and chemistry such as precision measurements, tests of fundamental physics, quantum simulation and information processing, quantum chemistry, and the physics of strongly correlated quantum matter. Laser cooling is usually infeasible in molecules because their rotational and vibrational transitions make is difficult to come up with a closed scattering cycle. Recently, a narrow range of diatomic molecules, one of which is CaF, has been shown to possess a convenient electronic structure and a highly-diagonal Franck-Condon matrix and thus be amenable to laser cooling. This thesis describes experiments on laser cooling of CaF radicals produced in a supersonic source. We first investigate the increased fluorescence when multi-frequency resonant light excites the molecules from the four hyperfine levels of the ground X²∑+(N = 1, v = 0) state to the first excited A²π½ (J’ = 1=2; v’ = 0) state. The number of photons scattered per molecule increases significantly from one or two in the single frequency case to more than 50 before the molecules get pumped into the X²∑+(N = 1; v = 1) state. We demonstrate laser cooling and slowing of CaF using counter-propagating laser light which causes the molecules to scatter more than a thousand photons on the X (N = 1, v = 0, 1) A (J’ = 1=2; v’ = 0) transition. The effect of the laser cooling is to slow a group of molecules from 600 ms-1 to about 580 ms-1 and to narrow their velocity distribution from an initial temperature of 3 K down to 300 mK. In addition, chirping the frequency of the cooling light to keep it on resonance with the decelerating molecules doubles the deceleration and further compresses the velocity distribution. The effect of the laser cooling is limited by the optical pumping of molecules in the X (N = 1, v = 2) state.Open Acces

Fluorescence-lifetime-limited trapping of Rydberg helium atoms on a chip

Metastable (1s)(2s) $^3{\rm S}_1$ helium atoms produced in a supersonic beam were excited to Rydberg-Stark states (with $n$ in the $27-30$ range) in a cryogenic environment and subsequently decelerated by, and trapped above, a surface-electrode decelerator. In the trapping experiments, the Rydberg atoms were brought to rest in 75~$\mu$s and over a distance of 33~mm and kept stationary for times $t_{\mathrm{trap}}$ in the $0-525$~$\mu$s range, before being re-accelerated for detection by pulsed field ionization. The use of a home-built valve producing short gas pulses with a duration of about 20~$\mu$s enabled the reduction of losses arising from collisions with atoms in the trailing part of the gas pulses. Cooling the decelerator to 4.7~K further suppressed losses by transitions induced by blackbody radiation and by collisions with atoms desorbing from the decelerator surface. The main contribution (60\%) to the atom loss during deceleration is attributed to the escape out of the decelerator moving traps of atoms having energies higher than the trap saddle point, spontaneous emission and collisions with atoms in the trailing part of the gas pulses causing each only about 20\% of the atom loss. At 4.7 K, the atom losses in the trapping phase of the experiments were found to be almost exclusively caused by spontaneous emission and the trap lifetimes were found to correspond to the natural lifetimes of the Rydberg-Stark states. Increasing the temperature to 100 K enhanced the trap losses by transitions stimulated by blackbody radiation

Opposite effects of the rotational and translational energy on the rates of ion-molecule reactions near 0 K0\,\text{K}: the D2++NH3\text{D}_2^++\text{NH}_3 and D2++ND3\text{D}_2^++\text{ND}_3 reactions

The ion-molecule reactions $\text{D}_2^++\text{NH}_3$ and $\text{D}_2^++\text{ND}_3$ are studied at low collision energies ($E_{\text{coll}}$ from zero to $\sim k_\textrm{B}\cdot 50\,\text{K}$), with the $\text{D}_2^+$ ions in the ground rovibrational state and for different rotational temperatures of the ammonia molecules, using the Rydberg-Stark merged-beam approach. Two different rotational temperatures ($\sim\,15\,\text{K}$ and $\sim\,40\,\text{K}$), measured by (2+1) resonance-enhanced multiphoton-ionization spectroscopy, are obtained by using a seeded supersonic expansion in He and a pure ammonia expansion, respectively. The experimental data reveal a strong enhancement of the rate coefficients at the lowest collision energies caused by the charge-dipole interaction. Calculations based on a rotationally adiabatic capture model accurately reproduce the observed kinetic-energy dependence of the rate coefficients. The rate coefficients increase with increasing rotational temperature of the ammonia molecules, which contradicts the expectation that rotational excitation should average the dipoles out. Moreover, these reactions exhibit a pronounced inverse kinetic isotope effect. The difference is caused by nuclear-spin-statistical factors, and the smaller rotational constants and tunneling splittings in $\text{ND}_3$.Comment: 14 pages, 8 figure

Cold Ion-Molecule Chemistry: The Very Different Reactions of He+ with CO and NO

The ion-molecule reactions He+ + CO → He + C+ + O and He+ + NO → He + N+ + O have been measured at collision energies between 0 and kB · 10 K. Strong variations of the rate coefficients are observed below kB · 5 K. The rate of the He+ + CO reaction decreases by ~30% whereas that of the He+ + NO reaction increases by a factor of ~1.5. These observations are interpreted in the realm of an adiabatic-channel capture model as arising from interactions between the ion charge and the dipole and quadrupole moments of CO and NO. We show that the different low-energy behavior of these reactions originates from the closed- vs. open-shell electronic structures of CO and NO

The Effect of the Molecular Dipole and Quadrupole Moments on Ion–Molecule Reaction Rates near 0 K

We review the results of our recent experimental and theoretical studies of gas-phase ion–molecule reactions involving the He+ ion at low collision energies (Ecoll), in the kB.(0 – 40) K range. To avoid heating of the ions by stray electric fields, the reactions are studied within the orbit of a Rydberg electron. We reach collision energies down to ~0 K by employing a merged-beam setup. In the case of a molecule with a dipole moment (e.g. ammonia), we observe a strong enhancement of the measured reaction yield with decreasing Ecoll. This enhancement is attributed to rotational states which experience linear negative Stark shifts in the electric field of the ion. When the molecule has no dipole moment but a negative quadrupole moment (e.g. N2), we observe a suppression of the total reaction yield at the lowest collision energy. Our results are interpreted with the aid of an adiabatic-channel model.ISSN:0009-429

Effects of the charge–dipole and charge–quadrupole interactions on the He+ + CO reaction rate coefficients at low collision energies

The reaction between He+ and CO forming He + C+ + O has been studied at collision energies in the range between 0 and kB ⋅ 25 K. These low collision energies are reached by measuring the reaction within the orbit of a Rydberg electron after merging a beam of He(n) Rydberg atoms and a supersonic beam of CO molecules with a rotational temperature of 6.5 K. The capture rate of the reaction drops by about 30% at collision energies below kB ⋅ 5 K. This behavior is analyzed in terms of the long-range charge–dipole and charge–quadrupole interactions using an adiabatic-channel capture model. Although the charge–dipole interaction has an effect on the magnitude of the rate coefficients, the effects of the charge–quadrupole interaction determine the main trend of the collision-energy dependence of the rate coefficients at low collision energies. The drop of the capture rate coefficient at low collision energies is attributed to the negative sign of the quadrupole moment of CO (Qzz = −2.839 D Å) and is caused by the |JM⟩ = |00⟩ and |1 ± 1⟩ rotational states of CO, which represent about 70% of the CO molecules at the rotational temperature of 6.5 K.ISSN:1367-263

Multipole-moment effects in ion-molecule reactions at low temperatures: part III - the He+ + CH4 and He+ + CD4 reactions at low collision energies and the effect of the charge-octupole interaction

We present experimental and theoretical studies of the He+ + CH4 and He+ + CD4 reactions at collision energies in the k(B).(0-10) K range. Helium atoms in a supersonic beam are excited to a low-field-seeking Rydberg-Stark state and merged with a supersonic beam of CH4 or CD4 using a curved surface-electrode deflector. The ion-molecule reactions are studied within the orbit of the helium Rydberg [He(n)] electron, which suppresses stray-electric-fields-induced heating and makes it possible to reach very low collision energies. The collision energy is varied by adjusting the velocity of the He(n) atoms with the surface deflector, keeping the velocity of the methane beam constant. The reaction product ions (C(H/D)(p)(+) with p epsilon {1,2,3}) are collected in a time-of-flight mass spectrometer and monitored as a function of the collision energy. No significant energy-dependence of the total reaction yields of either reactions is observed. The measured relative reaction rate coefficient for the He+ + CH4 reaction is approximately twice higher than the one for the He+ + CD4 reaction. The CH+, CH2+ and CH3+ (CD+, CD2+ and CD3+) ions were detected in ratios 0.28(+0.04) : 1.00(+0.11) : 0.11(+0.04) [0.35(+0.07) : 1.00(+0.16):0.04(-0.04)(+0.09)]. We also present calculations of the capture rate coefficients for the two reactions, in which the interaction between the charge of the helium ion and the octupole moment of the methane molecule is included. The rotational-state-specific capture rate coefficients are calculated for states with J = (0-3) at collision energies below k(B).15 K. After averaging over the rotational states of methane populated at the rotational temperature of the supersonic beam, the calculations only predict extremely weak enhancements (in the order of similar to 0.4%) of the rate coefficients compared to the Langevin rate constant k(L) over the collision-energy range considered.ISSN:1463-9084ISSN:1463-907

Cold ion chemistry within a Rydberg-electron orbit: test of the spectator role of the Rydberg electron in the He(n) + CO → C(n') + O + He reaction

Recently, a new method has been introduced to study ion-molecule reactions at very low collision energies, down to below kB ⋅ 1 K (Allmendinger et al 2016 ChemPhysChem 17 3596). To eliminate the acceleration of the ions by stray electric fields in the reaction volume, the reactions are observed within the orbit of a Rydberg electron with large principal quantum number n > 20. This electron is assumed not to influence the reaction taking place between the ion core and the neutral molecules. This assumption is tested here with the example of the He(n) + CO → C(n') + O + He reaction, which is expected to be equivalent to the He+ + CO → C+ + O + He reaction, using a merged-beam approach enabling measurements of relative reaction rates for collision energies Ecoll in the range from 0 to about kB ⋅ 25 K with a collision-energy resolution of ∼kB ⋅ 200 mK at Ecoll = 0. In contrast to the other ion-molecule reactions studied so far with this method, the atomic ion product (C+) is in its electronic ground state and does not have rotational and vibrational degrees of freedom so that the corresponding Rydberg product [C(n')] cannot decay by autoionization. Consequently, one can investigate whether the principal quantum number is effectively conserved, as would be expected in the spectator Rydberg-electron model. We measure the distribution of principal quantum numbers of the reactant He(n) and product C(n') Rydberg atoms by pulsed-field ionization following initial preparation of He(n) in states with n values between 30 and 45 and observe that the principal quantum number of the Rydberg electron is conserved during the reaction. This observation indicates that the Rydberg electron is not affected by the reaction, from which we can conclude that it does not affect the reaction either. This conclusion is strengthened by measurements of the collision-energy-dependent reaction yields at n = 30, 35 and 40, which exhibit the same behavior, i.e. a marked decrease below Ecoll ≈ kB ⋅ 5 K.ISSN:1367-263

Multipole-moment effects in ion–molecule reactions at low temperatures: Part II – charge– quadrupole-interaction-induced suppression of the He+ + N2 reaction at collision energies below kB10 K

We report on an experimental and theoretical investigation of the He+ + N2 reaction at collision energies in the range between 0 and kB·10 K. The reaction is studied within the orbit of a highly excited Rydberg electron after merging a beam of He Rydberg atoms (He(n), n is the principal quantum number), with a supersonic beam of ground-state N2 molecules using a surface-electrode Rydberg-Stark decelerator and deflector. The collision energy Ecoll is varied by changing the velocity of the He(n) atoms for a fixed velocity of the N2 beam and the relative yields of the ionic reaction products N+ and N2+ are monitored in a time-of-flight mass spectrometer. We observe a reduction of the total reaction-product yield of ∼30% as Ecoll is reduced from ≈kB·10 K to zero. An adiabatic capture model is used to calculate the rotational-state-dependent interaction potentials experienced by the N2 molecules in the electric field of the He+ ion and the corresponding collision-energy-dependent capture rate coefficients. The total collision-energy-dependent capture rate coefficient is then determined by summing over the contributions of the N2 rotational states populated at the 7.0 K rotational temperature of the supersonic beam. The measured and calculated rate coefficients are in good agreement, which enables us to attribute the observed reduction of the reaction rate at low collision energies to the negative quadrupole moment, Qzz, of the N2 molecules. The effect of the sign of the quadrupole moment is illustrated by calculations of the rotational-state-dependent capture rate coefficients for ion-molecule reactions involving N2 (negative Qzz value) and H2 (positive Qzz value) for |J, M〉 rotational states with J ≤ 5 (M is the quantum number associated with the projection of the rotational angular momentum vector J⃑ on the collision axis). With decreasing value of |M|, J⃑ gradually aligns perpendicularly to the collision axis, leading to increasingly repulsive (attractive) interaction potentials for diatomic molecules with positive (negative) Qzz values and to reaction rate coefficients that decrease (increase) with decreasing collision energies.ISSN:1463-9084ISSN:1463-907

Reaction of an Ion and a Free Radical near 0 K: He+ + NO → He + N+ + O

The reactions between ions and free radicals are among the fastest chemical reactions. They are predicted to proceed with large rates, even near 0 K, but so far, this prediction has not been verified experimentally. We report on measurements of the rate coefficient of the reaction between the ion He+ and the free radical NO at collision energies in the range between 0 and ∼ kB·10 K. To avoid heating of the ions by stray electric fields, the reaction is observed within the large orbit of a Rydberg electron of principal quantum number n ≥ 30, which shields the ion from external electric fields without affecting the reaction. Low collision energies are reached by merging a supersonic beam of He Rydberg atoms with a supersonic beam of NO molecules and adjusting their relative velocity using a chip-based Rydberg-Stark decelerator and deflector. We observe a strong enhancement of the reaction rate at collision energies below ∼kB·2 K. This enhancement is interpreted on the basis of adiabatic-channel capture-rate calculations as arising from the near-degenerate rotational levels of opposite parity resulting from the Λ-doubling in the X 2Π1/2 ground state of NO. With these new results, we examine the reliability of broadly used approximate analytic expressions for the thermal rate constants of ion-molecule reactions at low temperatures.ISSN:1089-5639ISSN:1520-521