Chemical bonding dictates drastic critical temperature difference in two seemingly identical superconductors.

Though YB6 and LaB6 share the same crystal structure, atomic valence electron configuration, and phonon modes, they exhibit drastically different phonon-mediated superconductivity. YB6 superconducts below 8.4 K, giving it the second-highest critical temperature of known borides, second only to MgB2. LaB6 does not superconduct until near-absolute zero temperatures (below 0.45 K), however. Though previous studies have quantified the canonical superconductivity descriptors of YB6's greater Fermi-level (Ef) density of states and higher electron-phonon coupling (EPC), the root of this difference has not been assessed with full detail of the electronic structure. Through chemical bonding, we determine low-lying, unoccupied 4f atomic orbitals in lanthanum to be the key difference between these superconductors. These orbitals, which are not accessible in YB6, hybridize with π B-B bonds and bring this π-system lower in energy than the σ B-B bonds otherwise at Ef. This inversion of bands is crucial: the optical phonon modes we show responsible for superconductivity cause the σ-orbitals of YB6 to change drastically in overlap, but couple weakly to the π-orbitals of LaB6. These phonons in YB6 even access a crossing of electronic states, indicating strong EPC. No such crossing in LaB6 is observed. Finally, a supercell (the M k-point) is shown to undergo Peierls-like effects in YB6, introducing additional EPC from both softened acoustic phonons and the same electron-coupled optical modes as in the unit cell. Overall, we find that LaB6 and YB6 have fundamentally different mechanisms of superconductivity, despite their otherwise near-identity.

Fully Saturated Hydrocarbons as Hosts of Optical Cycling Centers.

Designing closed, laser-induced optical cycling transitions in trapped atoms or molecules is useful for quantum information processing, precision measurement, and quantum sensing. Larger molecules that feature such closed transitions are particularly desirable, as the increased degrees of freedom present new structures for optical control and enhanced measurements. The search for molecules with robust optical cycling centers is a challenge which requires design principles beyond trial-and-error. Two such principles are proposed for the particular M-O-R framework, where M is an alkaline earth metal radical, and R is a ligand: (1) Large, saturated hydrocarbons can serve as ligands, R, due to a substantial HOMO-LUMO gap that encloses the cycling transition, so long as the R group is rigid. (2) Electron-withdrawing groups, via induction, can enhance Franck-Condon factors (FCFs) of the optical cycling transition, as long as they do not disturb the locally linear structure in the M-O-R motif. With these tools in mind, larger molecules can be trapped and used as optical cycling centers, sometimes with higher FCFs than smaller molecules.

Franck-Condon Tuning of Optical Cycling Centers by Organic Functionalization.

Laser induced electronic excitations that spontaneously emit photons and decay directly to the initial ground state ("optical cycling transitions") are used in quantum information and precision measurement for state initialization and readout. To extend this primarily atomic technique to large, organic compounds, we theoretically investigate optical cycling of alkaline earth phenoxides and their functionalized derivatives. We find that optical cycle leakage due to wave function mismatch is low in these species, and can be further suppressed by using chemical substitution to boost the electron-withdrawing strength of the aromatic molecular ligand through resonance and induction effects. This provides a straightforward way to use chemical functional groups to construct optical cycling moieties for laser cooling, state preparation, and quantum measurement.

Pattern-free generation and quantum mechanical scoring of ring-chain tautomers.

In contrast to the computational generation of conventional tautomers, the analogous operation that would produce ring-chain tautomers is rarely available in cheminformatics codes. This is partly due to the perceived unimportance of ring-chain tautomerism and partly because specialized algorithms are required to realize the non-local proton transfers that occur during ring-chain rearrangement. Nevertheless, for some types of organic compounds, including sugars, warfarin analogs, fluorescein dyes and some drug-like compounds, ring-chain tautomerism cannot be ignored. In this work, a novel ring-chain tautomer generation algorithm is presented. It differs from previously proposed solutions in that it does not rely on hard-coded patterns of proton migrations and bond rearrangements, and should therefore be more general and maintainable. We deploy this algorithm as part of a workflow which provides an automated solution for tautomer generation and scoring. The workflow identifies protonatable and deprotonatable sites in the molecule using a previously described approach based on rapid micro-pKa prediction. These data are used to distribute the active protons among the protonatable sites exhaustively, at which point alternate resonance structures are considered to obtain pairs of atoms with opposite formal charge. These pairs are connected with a single bond and a 3D undistorted geometry is generated. The scoring of the generated tautomers is performed with a subsequent density functional theory calculation employing an implicit solvent model. We demonstrate the performance of our workflow on several types of organic molecules known to exist in ring-chain tautomeric equilibria in solution. In particular, we show that some ring-chain tautomers not found using previously published algorithms are successfully located by ours.

Surface chemical trapping of optical cycling centers.

Quantum information processors based on trapped atoms utilize laser-induced optical cycling transitions for state preparation and measurement. These transitions consist of an electronic excitation from the ground to an excited state and a decay back to the initial ground state, associated with a photon emission. While this technique has been used primarily with atoms, it has also recently been shown to work for some divalent metal hydroxides (e.g. SrOH) and alkoxides (e.g. SrOCH3). This extension to molecules is possible because these molecules feature nearly isolated, atomic-like ground and first-excited electronic states centered on the radical metal atom. We theoretically investigate the extension of this idea to a larger scale by growing the alkyl group, R, beyond the initial methyl group, CH3, while preserving the isolated and highly vertical character of the electronic excitation on the radical metal atom, M. Theory suggests that in the limit as the size of the ligand carbon chain increases, it can be considered a functionalized diamond (or cubic boron nitride) surface. Several requirements must be observed for the cycling centers to function when bound to the surface. First, the surface must have a significant band gap that fully encapsulates both the ground and excited states of the cycling center. Second, while the surface lattice imposes strict limits on the achievable spacing between the SrO- groups, at high coverage, SrO- centers can interact, and show geometric changes and/or electronic state mixing. We show that the coverage of the diamond surface with SrO- cycling centers needs to be significantly sub-monolayer for the functionality of the cycling center to be preserved. Having the lattice-imposed spatial control of SrO- placements will allow nanometer-scale proximity between qubits and will eliminate the need for atom traps for localized cycling emitters. Our results also imply that a functionalization could be done on a scanning microscope tip for local quantum sensing or on photonic structures for optically-mediated quantum information processing.

Cobalt Metallopeptide Electrocatalyst for the Selective Reduction of Nitrite to Ammonium.

A cobalt-tripeptide complex (CoGGH) is developed as an electrocatalyst for the selective six-electron, eight-proton reduction of nitrite to ammonium in aqueous buffer near neutral pH. The onset potential for nitrite reduction occurs at -0.65 V vs Ag/AgCl (1 M KCl). Controlled potential electrolysis at -0.90 V generates ammonium with a faradaic efficiency of 90 ± 3% and a turnover number of 3550 ± 420 over 5.5 h. CoGGH also catalyzes the reduction of the proposed intermediates nitric oxide and hydroxylamine to ammonium. These results reveal that a simple metallopeptide is an active functional mimic of the complex enzymes cytochrome c nitrite reductase and siroheme-containing nitrite reductase.

Characterization of Azirine and Its Structural Isomers.

The structures and spectroscopic properties of azirine (C2H3N), a nitrogen-containing three-membered cyclic molecule, and its isomers were studied with state-of-the-art ab initio quantum chemical methods. Azirine is isomeric with methyl cyanide (CH3CN) and methyl isocyanide (CH3NC)-both observed in the star-forming regions of Sgr B2. In this study, we characterize the stationary points on the potential energy surface, relative energies, dipole moments, rotational constants, and harmonic vibrational frequencies of the 2 H-azirine ( a), 1 H-2,2 H-azirine ( b, carbene isomer), and 1 H-azirine ( c) cyclic isomers. The CCSD(T) method and density functional theory (DFT), using the ωB97-X functional, along with Dunning's cc-pVXZ (X = T and Q) basis sets were used to optimize molecular geometries and calculate vibrational frequencies. The 2 H-azirine, an imine isomer ( a), was found to be the lowest in energy among the cyclic isomers, followed by the carbene isomer ( b), and last the 1 H-azirine, an enamine isomer ( c). All three cyclic isomers have a C s symmetry equilibrium structure. Azirines, if identified (three linear C2H3N isomers are already identified in the same source toward the galactic center, Sgr B2), would be the first nitrogen-containing cyclic molecules identified in an astronomical observation.

Extending the Large Molecule Limit: The Role of Fermi Resonance in Developing a Quantum Functional Group.

Polyatomic molecules equipped with optical cycling centers (OCCs), enabling continuous photon scattering during optical excitation, are exciting candidates for advancing quantum information science. However, as these molecules grow in size and complexity, the interplay of complex vibronic couplings on optical cycling becomes a critical but relatively unexplored consideration. Here, we present an extensive exploration of Fermi resonances in large-scale OCC-containing molecules using high-resolution dispersed laser-induced fluorescence and excitation spectroscopy. These resonances manifest as vibrational coupling leading to intensity borrowing by combination bands near optically active harmonic bands, which require additional repumping lasers for effective optical cycling. To mitigate these effects, we explore altering the vibrational energy level spacing through substitutions on the phenyl ring or changes in the OCC itself. While the complete elimination of vibrational coupling in complex molecules remains challenging, our findings highlight significant mitigation possibilities, opening new avenues for optimizing optical cycling in large polyatomic molecules.

Laser Spectroscopy of Aromatic Molecules with Optical Cycling Centers: Strontium(I) Phenoxides.

We report the production and spectroscopic characterization of strontium(I) phenoxide (SrOC6H5 or SrOPh) and variants featuring electron-withdrawing groups designed to suppress vibrational excitation during spontaneous emission from the electronically excited state. Optical cycling closure of these species, which is the decoupling of the vibrational state changes from spontaneous optical decay, is found by dispersed laser-induced fluorescence spectroscopy to be high, in accordance with theoretical predictions. A high-resolution, rotationally resolved laser excitation spectrum is recorded for SrOPh, allowing the estimation of spectroscopic constants and identification of candidate optical cycling transitions for future work. The results confirm the promise of strontium phenoxides for laser cooling and quantum state detection at the single-molecule level.

Functionalizing aromatic compounds with optical cycling centres.

Molecular design principles provide guidelines for augmenting a molecule with a smaller group of atoms to realize a desired property or function. We demonstrate that these concepts can be used to create an optical cycling centre, the Ca(I)-O unit, that can be attached to a number of aromatic ligands, enabling the scattering of many photons from the resulting molecules without changing the molecular vibrational state. Such capability plays a central role in quantum state preparation and measurement, as well as laser cooling and trapping, and is therefore a prerequisite for many quantum science and technology applications. We provide further molecular design principles that indicate the ability to optimize and expand this work to an even broader class of molecules. This represents a great step towards a quantum functional group, which may serve as a generic qubit moiety that can be attached to a wide range of molecular structures and surfaces.

Pathway toward Optical Cycling and Laser Cooling of Functionalized Arenes.

Rapid and repeated photon cycling has enabled precision metrology and the development of quantum information systems using atoms and simple molecules. Extending optical cycling to structurally complex molecules would provide new capabilities in these areas, as well as in ultracold chemistry. Increased molecular complexity, however, makes realizing closed optical transitions more difficult. Building on already established strong optical cycling of diatomic, linear triatomic, and symmetric top molecules, recent work has pointed the way to cycling of larger molecules, including phenoxides. The paradigm for these systems is an optical cycling center bonded to a molecular ligand. Theory has suggested that cycling may be extended to even larger ligands, like naphthalene, pyrene, and coronene. Herein, we study optical excitation and fluorescent vibrational branching of CaO-[Formula: see text], SrO-[Formula: see text], and CaO-[Formula: see text] and find only weak decay to excited vibrational states, indicating a promising path to full quantum control and laser cooling of large arene-based molecules.

Analog quantum simulation of chemical dynamics.

Ultrafast chemical reactions are difficult to simulate because they involve entangled, many-body wavefunctions whose computational complexity grows rapidly with molecular size. In photochemistry, the breakdown of the Born-Oppenheimer approximation further complicates the problem by entangling nuclear and electronic degrees of freedom. Here, we show that analog quantum simulators can efficiently simulate molecular dynamics using commonly available bosonic modes to represent molecular vibrations. Our approach can be implemented in any device with a qudit controllably coupled to bosonic oscillators and with quantum hardware resources that scale linearly with molecular size, and offers significant resource savings compared to digital quantum simulation algorithms. Advantages of our approach include a time resolution orders of magnitude better than ultrafast spectroscopy, the ability to simulate large molecules with limited hardware using a Suzuki-Trotter expansion, and the ability to implement realistic system-bath interactions with only one additional interaction per mode. Our approach can be implemented with current technology; e.g., the conical intersection in pyrazine can be simulated using a single trapped ion. Therefore, we expect our method will enable classically intractable chemical dynamics simulations in the near term.

Optical Cycling Functionalization of Arenes.

Closed, laser-induced optical transitions ("optical cycling transitions") of molecules can be used for state preparation and measurement in quantum information science and quantum sensing. Increasingly complex molecular species supporting optical cycling can provide new capabilities for quantum science, and it is not clear if there is a limit on their size or complexity. We explore Ca-O-L molecular constructs to support the optical cycling center, Ca, with ligands, L, being arenes. We find that L can be as large as coronene (i.e., CaOC24H11) without losing the diagonality of the Franck-Condon factor (FCF). Furthermore, L can be substituted with electron-withdrawing groups to improve the FCF. Larger L, beyond ∼7 rings, can disrupt the diagonality of the FCF by closing the HOMO-LUMO ligand electronic state gap and reordering with the local states on the cycling center. Overall, we find that optical cycling can be retained for arenes, and we offer a principle for their design.