Large vibrationally induced parity violation effects in CHDBrI.

The isotopically chiral molecular ion CHDBrI+ is identified as an exceptionally promising candidate for the detection of parity violation in vibrational transitions. The largest predicted parity-violating frequency shift reaches 1.8 Hz for the hydrogen wagging mode which has a sub-Hz natural line width and its vibrational frequency auspiciously lies in the available laser range. In stark contrast to this result, the parent neutral molecule is two orders of magnitude less sensitive to parity violation. The origin of this effect is analyzed and explained. Precision vibrational spectroscopy of CHDBrI+ is feasible as it is amenable to preparation at internally low temperatures and resistant to predissociation, promoting long interrogation times (Landau et al., J. Chem. Phys., 2023, 159, 114307). The intersection of these properties in this molecular ion places the first observation of parity violation in chiral molecules within reach.

Chiral molecule candidates for trapped ion spectroscopy by ab initio calculations: From state preparation to parity violation.

Parity non-conservation (PNC) due to the weak interaction is predicted to give rise to enantiomer dependent vibrational constants in chiral molecules, but the phenomenon has so far eluded experimental observation. The enhanced sensitivity of molecules to physics beyond the Standard Model (BSM) has led to substantial advances in molecular precision spectroscopy, and these may be applied to PNC searches as well. Specifically, trapped molecular ion experiments leverage the universality of trapping charged particles to optimize the molecular ion species studied toward BSM searches, but in searches for PNC, only a few chiral molecular ion candidates have been proposed so far. Importantly, viable candidates need to be internally cold, and their internal state populations should be detectable with high quantum efficiency. To this end, we focus on molecular ions that can be created by near threshold resonant two-photon ionization and detected via state-selective photo-dissociation. Such candidates need to be stable in both charged and neutral chiral versions to be amenable to these methods. Here, we present a collection of suitable chiral molecular ion candidates we have found, including CHDBrI+ and CHCaBrI+, that fulfill these conditions according to our ab initio calculations. We find that organo-metallic species have low ionization energy as neutrals and relatively high dissociation thresholds. Finally, we compute the magnitude of the PNC values for vibrational transitions for some of these candidates. An experimental demonstration of state preparation and readout for these candidates will be an important milestone toward measuring PNC in chiral molecules for the first time.

An improved bound on the electron's electric dipole moment.

The imbalance of matter and antimatter in our Universe provides compelling motivation to search for undiscovered particles that violate charge-parity symmetry. Interactions with vacuum fluctuations of the fields associated with these new particles will induce an electric dipole moment of the electron (eEDM). We present the most precise measurement yet of the eEDM using electrons confined inside molecular ions, subjected to a huge intramolecular electric field, and evolving coherently for up to 3 seconds. Our result is consistent with zero and improves on the previous best upper bound by a factor of ~2.4. Our results provide constraints on broad classes of new physics above [Formula: see text] electron volts, beyond the direct reach of the current particle colliders or those likely to be available in the coming decades.

Experimental Constraint on Axionlike Particles over Seven Orders of Magnitude in Mass.

We use our recent electric dipole moment (EDM) measurement data to constrain the possibility that the HfF^{+} EDM oscillates in time due to interactions with candidate dark matter axionlike particles (ALPs). We employ a Bayesian analysis method which accounts for both the look-elsewhere effect and the uncertainties associated with stochastic density fluctuations in the ALP field. We find no evidence of an oscillating EDM over a range spanning from 27 nHz to 400 mHz, and we use this result to constrain the ALP-gluon coupling over the mass range 10^{-22}-10^{-15} eV. This is the first laboratory constraint on the ALP-gluon coupling in the 10^{-17}-10^{-15} eV range, and the first laboratory constraint to properly account for the stochastic nature of the ALP field.

Phase protection of Fano-Feshbach resonances.

Decay of bound states due to coupling with free particle states is a general phenomenon occurring at energy scales from MeV in nuclear physics to peV in ultracold atomic gases. Such a coupling gives rise to Fano-Feshbach resonances (FFR) that have become key to understanding and controlling interactions-in ultracold atomic gases, but also between quasiparticles, such as microcavity polaritons. Their energy positions were shown to follow quantum chaotic statistics. In contrast, their lifetimes have so far escaped a similarly comprehensive understanding. Here, we show that bound states, despite being resonantly coupled to a scattering state, become protected from decay whenever the relative phase is a multiple of π. We observe this phenomenon by measuring lifetimes spanning four orders of magnitude for FFR of spin-orbit excited molecular ions with merged beam and electrostatic trap experiments. Our results provide a blueprint for identifying naturally long-lived states in a decaying quantum system.

Second-Scale Coherence Measured at the Quantum Projection Noise Limit with Hundreds of Molecular Ions.

Cold molecules provide an excellent platform for quantum information, cold chemistry, and precision measurement. Certain molecules have enhanced sensitivity to beyond standard model physics, such as the electron's electric dipole moment (eEDM). Molecular ions are easily trappable and are therefore particularly attractive for precision measurements where sensitivity scales with interrogation time. Here, we demonstrate a spin precession measurement with second-scale coherence at the quantum projection noise (QPN) limit with hundreds of trapped molecular ions, chosen for their sensitivity to the eEDM rather than their amenability to state control and readout. Orientation-resolved resonant photodissociation allows us to simultaneously measure two quantum states with opposite eEDM sensitivity, reaching the QPN limit and fully exploiting the high count rate and long coherence.

Enhancing radical molecular beams by skimmer cooling.

A high-intensity supersonic beam source has been a key component in studies of molecular collisions, molecule-surface interaction, chemical reactions, and precision spectroscopy. However, the molecular density available for experiments in a downstream science chamber is limited by skimmer clogging, which constrains the separation between a valve and a skimmer to at least several hundred nozzle diameters. A recent experiment (Sci. Adv., 2017, 3, e1602258) has introduced a new strategy to address this challenge: when a skimmer is cooled to a temperature below the freezing point of the carrier gas, skimmer clogging can be effectively suppressed. We go beyond this proof-of-principle work in several key ways. Firstly, we apply the skimmer cooling approach to discharge-produced radical and metastable beams entrained in a carrier gas. We also identify two different processes for skimmer clogging mitigation-shockwave suppression at temperatures around the carrier gas freezing point and diffusive clogging at even lower temperatures. With the carrier clogging removed, we now fully optimize the production of entrained species such as hydroxyl radicals, resulting in a gain of 30 in density over the best commercial devices. The gain arises from both clogging mitigation and favorable geometry with a much shorter valve-skimmer distance.

Molecular beam brightening by shock-wave suppression.

Supersonic beams are a prevalent source of cold molecules used in the study of chemical reactions, atom interferometry, gas-surface interactions, precision spectroscopy, molecular cooling, and more. The triumph of this method emanates from the high densities produced in relation to other methods; however, beam density remains fundamentally limited by interference with shock waves reflected from collimating surfaces. We show experimentally that this shock interaction can be reduced or even eliminated by cryocooling the interacting surface. An increase of nearly an order of magnitude in beam density was measured at the lowest surface temperature, with no further fundamental limitation reached. Visualization of the shock waves by plasma discharge and reproduction with direct simulation Monte Carlo calculations both indicate that the suppression of the shock structure is partially caused by lowering the momentum flux of reflected particles and significantly enhanced by the adsorption of particles to the surface. We observe that the scaling of beam density with source pressure is recovered, paving the way to order-of-magnitude brighter, cold molecular beams.

Adiabatic Variational Theory for Cold Atom-Molecule Collisions: Application to a Metastable Helium Atom Colliding with ortho- and para-Hydrogen Molecules.

We recently developed an adiabatic theory for cold molecular collision experiments. In our previous application of this theory ( Pawlak, M.; et al. J. Chem. Phys. 2015 , 143 , 074114 ), we assumed that during the experiment the collision of an atom with a diatom takes place when the diatom is in the ground rotational state and is located in a plane. In this paper, we present how the variational approach of the adiabatic theory for low-temperature collision experiments can be used for the study a 5D collision between the atom and the diatomic molecule with no limitations on its rotational quantum states and no plane restrictions. Moreover, we show here the dramatic differences in the measured reaction rates of He(23S1) + ortho/para-H2 → He(1s2) + ortho/para-H2+ + e- resulting from the anisotropic long-range interactions in the reaction. In collisions of metastable helium with molecular hydrogen in the ground rotational state, the isotropic potential term dominates the dynamics. When the collision is with molecular hydrogen in the first excited rotational state, the nonisotropic interactions play an important role in the dynamics. The agreement of our results with the latest experimental findings ( Klein , A. ; et al. Nat. Phys. 2017 , 13 , 35 - 38 ) is very good.

Photoassociation Spectroscopy in Penning Ionization Reactions at Sub-Kelvin Temperatures.

Penning ionization reactions in merged beams with precisely controlled collision energies have been shown to accurately probe quantum mechanical effects in reactive collisions. A complete microscopic understanding of the reaction is, however, faced with two major challenges-the highly excited character of the reaction's entrance channel and the limited precision of even the best state-of-the-art ab initio potential energy surfaces. Here, we suggest photoassociation spectroscopy as a tool to identify the character of orbiting resonances in the entrance channel and probe the ionization width as a function of interparticle separation. We introduce the basic concept, using the example of metastable helium and argon, and discuss the general conditions under which this type of spectroscopy will be successful.

Molecular hydrogen interacts more strongly when rotationally excited at low temperatures leading to faster reactions.

The role of internal molecular degrees of freedom, such as rotation, has scarcely been explored experimentally in low-energy collisions despite their significance to cold and ultracold chemistry. Particularly important to astrochemistry is the case of the most abundant molecule in interstellar space, hydrogen, for which two spin isomers have been detected, one of which exists in its rotational ground state whereas the other is rotationally excited. Here we demonstrate that quantization of molecular rotation plays a key role in cold reaction dynamics, where rotationally excited ortho-hydrogen reacts faster due to a stronger long-range attraction. We observe rotational state-dependent non-Arrhenius universal scaling laws in chemi-ionization reactions of para-H2 and ortho-H2 by He(2(3)P2), spanning three orders of magnitude in temperature. Different scaling laws serve as a sensitive gauge that enables us to directly determine the exact nature of the long-range intermolecular interactions. Our results show that the quantum state of the molecular rotor determines whether or not anisotropic long-range interactions dominate cold collisions.

Adiabatic theory for anisotropic cold molecule collisions.

We developed an adiabatic theory for cold anisotropic collisions between slow atoms and cold molecules. It enables us to investigate the importance of the couplings between the projection states of the rotational motion of the atom about the molecular axis of the diatom. We tested our theory using the recent results from the Penning ionization reaction experiment (4)He(1s2s (3)S) + HD(1s(2)) → (4)He(1s(2)) + HD(+)(1s) + e(-) [Lavert-Ofir et al., Nat. Chem. 6, 332 (2014)] and demonstrated that the couplings have strong effect on positions of shape resonances. The theory we derived provides cross sections which are in a very good agreement with the experimental findings.

Observation of the isotope effect in sub-kelvin reactions.

Quantum phenomena in the translational motion of reactants, which are usually negligible at room temperature, can dominate reaction dynamics at low temperatures. In such cold conditions, even the weak centrifugal force is enough to create a potential barrier that keeps reactants separated. However, reactions may still proceed through tunnelling because, at low temperatures, wave-like properties become important. At certain de Broglie wavelengths, the colliding particles can become trapped in long-lived metastable scattering states, leading to sharp increases in the total reaction rate. Here, we show that these metastable states are responsible for a dramatic, order-of-magnitude-strong, quantum kinetic isotope effect by measuring the absolute Penning ionization reaction rates between hydrogen isotopologues and metastable helium down to 0.01 K. We demonstrate that measurements of a single isotope are insufficient to constrain ab initio calculations, making the kinetic isotope effect in the cold regime necessary to remove ambiguity among possible potential energy surfaces.