Role of Polarization Interactions in the Formation of Dipole-Bound States.

Even though there is a critical dipole moment required to support a dipole-bound state (DBS), how molecular polarizability may influence the formation of DBSs is not well understood. Pyrrolide, indolide, and carbazolide provide an ideal set of anions to systematically examine the role of polarization interactions in the formation of DBSs. Here, we report an investigation of carbazolide using cryogenic photodetachment spectroscopy and high-resolution photoelectron spectroscopy (PES). A polarization-assisted DBS is observed at 20 cm-1 below the detachment threshold for carbazolide, even though the carbazolyl neutral core has a dipole moment (2.2 D) smaller than the empirical critical value (2.5 D) to support a dipole-bound state. Photodetachment spectroscopy reveals nine vibrational Feshbach resonances of the DBS, as well as three intense and broad shape resonances. The electron affinity of carbazolyl is measured accurately to be 2.5653 ± 0.0004 eV (20,691 ± 3 cm-1). The combination of photodetachment spectroscopy and resonant PES allows fundamental frequencies for 14 vibrational modes of carbazolyl to be measured. The three shape resonances are due to above-threshold excitation to the three low-lying electronic states (S1-S3) of carbazolide. Resonant PES of the shape resonances is dominated by autodetachment processes. Ultrafast relaxation from the S2 and S3 states to S1 is observed, resulting in constant kinetic energy features in the resonant PES. The current study provides decisive information about the role that polarization plays in the formation of DBSs, as well as rich spectroscopic information about the carbazolide anion and the carbazolyl radical.

Observation of a Symmetry-Forbidden Excited Quadrupole-Bound State.

We report the observation of a symmetry-forbidden excited quadrupole-bound state (QBS) in the tetracyanobenzene anion (TCNB-) using both photoelectron and photodetachment spectroscopies of cryogenically-cooled anions. The electron affinity of TCNB is accurately measured as 2.4695 eV. Photodetachment spectroscopy of TCNB- reveals selected symmetry-allowed vibronic transitions to the QBS, but the ground vibrational state was not observed because the transition from the ground state of TCNB- (Au symmetry) to the QBS (Ag symmetry) is triply forbidden by the electric and magnetic dipoles and the electric quadrupole. The binding energy of the QBS is found to be 0.2206 eV, which is unusually large due to strong correlation and polarization effects. A centrifugal barrier is observed for near-threshold autodetachment, as well as relaxations from the QBS vibronic levels to the ground and a valence excited state of TCNB-. The current study shows a rare example where symmetry selection rules, rather than the Franck-Condon principle, govern vibronic transitions to a nonvalence state in an anion.

In search of molecular ions for optical cycling: a difficult road.

Optical cycling, a continuous photon scattering off atoms or molecules, plays a central role in the quantum information science. While optical cycling has been experimentally achieved for many neutral species, few molecular ions have been investigated. We present a systematic theoretical search for diatomic molecular ions suitable for optical cycling using equation-of-motion coupled-cluster methods. Inspired by the electronic structure patterns of laser-cooled neutral molecules, we establish the design principles for molecular ions and explore various possible cationic molecular frameworks. The results show that finding a perfect molecular ion for optical cycling is challenging, yet possible. Among various possible diatomic molecules we suggest several candidates, which require further attention from both theory and experiment: YF+, SiO+, PN+, SiBr+, and BO+.

Photodetachment spectroscopy and resonant photoelectron imaging of the 2-naphthoxide anion via dipole-bound excited states.

We report a photodetachment spectroscopy and high-resolution resonant photoelectron imaging study of cryogenically cooled 2-naphthoxide anions (C10H7O-). The photodetachment spectrum revealed a dipole-bound state (DBS) 202(4) cm-1 below the detachment threshold and 38 resonances corresponding to the vibrational levels of the DBS. By tuning the detachment laser to these above-threshold resonances, we obtained 38 resonantly enhanced photoelectron spectra, which were highly non-Franck-Condon as a result of mode-selective vibrational autodetachment from the DBS. The resonances were assigned by comparing the resonant and non-resonant photoelectron spectra, assisted by the computed vibrational frequencies. Specifically, vibrational features with low Franck-Condon factors or from Franck-Condon-forbidden vibrational modes were significantly enhanced in the resonant photoelectron spectra, resulting in much richer spectroscopic information. The electron affinity of the 2-naphthoxy radical was measured accurately to be 19 387(4) cm-1 or 2.4037(5) eV. In addition, a total of 17 vibrational frequencies were obtained for the 2-naphthoxy radical. In particular, seven Franck-Condon-forbidden out-of-plane bending modes, including the two lowest frequency modes (ν48 at 102 cm-1 and ν47 at 171 cm-1), were observed, demonstrating the advantages of combining photodetachment spectroscopy and resonant photoelectron spectroscopy in obtaining vibrational information for polar radical species via DBS.

Tautomer-Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions.

Tautomers of the nucleobases play fundamental roles in spontaneous mutations of DNA. Tautomers of neutral cytosine have been studied in the gas phase, but much less is known about charged species. Here, we report the observation and characterization of three tautomers of deprotonated cytosine anions, [trans-keto-amino-N3H-H8b] (tKAN3H8b- ), [cis-keto-amino-N3H-H8a] (cKAN3H8a- ) and [keto-amino-H] (KAN1- ), produced by electrospray ionization. Excited dipole-bound states (DBSs) are uncovered for the three anions by photodetachment spectroscopy. Excitations to selected DBS vibrational levels of cKAN3H8a- and tKAN3H8b- yield tautomer-specific resonant photoelectron spectra. The current study provides further insight into tautomerism of cytosine and suggests a new method to study the tautomers of nucleobases using electrospray ionization and anion spectroscopy.

Dipole-bound excited states and resonant photoelectron imaging of phenoxide and thiophenoxide anions.

We report photodetachment and resonant photoelectron-imaging studies of cryogenically cooled phenoxide (C6H5O-) and thiophenoxide (C6H5S-) anions. In a previous study [H. T. Liu et al. Angew. Chem., Int. Ed. 52, 8976 (2013)], a dipole-bound excited state was observed for C6H5O- at 97 cm-1 below the detachment threshold. Eight resonant photoelectron spectra were obtained via excitations to eight vibrational levels of the dipole-bound state (DBS) followed by autodetachment. Here we present a complete photodetachment spectrum of C6H5O- covering a spectral range 2600 cm-1 above the detachment threshold and revealing nine additional vibrational resonances of the DBS. We also report the first observation of a dipole-bound excited state for C6H5S-, 39 cm-1 below its detachment threshold of 18 982 cm-1. Photodetachment spectroscopy covering a spectral range 1500 cm-1 above the threshold reveals twelve vibrational resonances for the DBS of C6H5S-. By tuning the detachment laser to the vibrational resonances in the DBS of C6H5O- and C6H5S-, we obtain highly non-Franck-Condon resonant photoelectron spectra, as a result of mode-selectivity and the Δv = -1 propensity rule for vibrational autodetachment. Five new fundamental vibrational frequencies are obtained for the ground state of the C6H5O (X 2B1) radical. Intramolecular inelastic scattering is observed in some of the resonant photoelectron spectra, leading to the excitation of the Franck-Condon-inactive lowest-frequency bending mode (ν20) of C6H5O. The first excited state of C6H5O (A 2B2) is observed to be 0.953 eV above the ground state. Twelve resonant photoelectron spectra are obtained for C6H5S-, allowing the measurements of seven fundamental vibrational frequencies of the C6H5S radical, whereas the non-resonant photoelectron spectrum exhibits only a single Franck-Condon active mode. The current study again demonstrates that the combination of photodetachment spectroscopy and resonant photoelectron spectroscopy is a powerful technique to obtain vibrational information about polar radical species.

Observation of Excited Quadrupole-Bound States in Cold Anions.

We report the first observation of an excited quadrupole-bound state (QBS) in an anion. High-resolution photoelectron imaging of cryogenically cooled 4-cyanophenoxide (4CP^{-}) anions yields an electron detachment threshold of 24 927 cm^{-1}. The photodetachment spectrum reveals a resonant transition 20 cm^{-1} below the detachment threshold, which is attributed to an excited QBS of 4CP^{-} because neutral 4CP has a large quadrupole moment with a negligible dipole moment. The QBS is confirmed by observation of seventeen above-threshold resonances due to autodetachment from vibrational levels of the QBS.

Conformation-selective resonant photoelectron imaging from dipole-bound states of cold 3-hydroxyphenoxide.

We report a photoelectron imaging and photodetachment study of cryogenically cooled 3-hydroxyphenoxide (3HOP) anions, m-HO(C6H4)O-. In a previous preliminary study, two conformations of the cold 3HOP anions with different dipole bound states were observed [D. L. Huang et al., J. Phys. Chem. Lett. 6, 2153 (2015)]. Five near-threshold vibrational resonances were revealed in the photodetachment spectrum from the dipole-bound excited states of the two conformations. Here, we report a more extensive investigation of the two conformers with observation of thirty above-threshold vibrational resonances in a wide spectral range between 18 850 and 19 920 cm-1 (∼1000 cm-1 above the detachment thresholds). By tuning the detachment laser to the vibrational resonances in the photodetachment spectrum, high-resolution conformation-selective resonant photoelectron images are obtained. Using information of the autodetachment channels and theoretical vibrational frequencies, we are able to assign the resonant peaks in the photodetachment spectrum: seventeen are assigned to vibrational levels of anti-3HOP, eight to syn-3HOP, and five to overlapping vibrational levels of both conformers. From the photodetachment spectrum and the conformation-selective resonant photoelectron spectra, we have obtained fourteen fundamental vibrational frequencies for the neutral syn- and anti-m-HO(C6H4)O⋅ radicals. The possibility to produce conformation-selected neutral beams using resonant photodetachment via dipole-bound excited states of anions is discussed.

Communication: Vibrationally resolved photoelectron spectroscopy of the tetracyanoquinodimethane (TCNQ) anion and accurate determination of the electron affinity of TCNQ.

Tetracyanoquinodimethane (TCNQ) is widely used as an electron acceptor to form highly conducting organic charge-transfer solids. Surprisingly, the electron affinity (EA) of TCNQ is not well known and has never been directly measured. Here, we report vibrationally resolved photoelectron spectroscopy (PES) of the TCNQ(-) anion produced using electrospray and cooled in a cryogenic ion trap. Photoelectron spectrum taken at 354.7 nm represents the detachment transition from the ground state of TCNQ(-) to that of neutral TCNQ with a short vibrational progression. The EA of TCNQ is measured accurately to be 3.383 ± 0.001 eV (27,289 ± 8 cm(-1)), compared to the 2.8 ± 0.1 eV value known in the literature and measured previously using collisional ionization technique. In addition, six vibrational peaks are observed in the photoelectron spectrum, yielding vibrational frequencies for three totally symmetric modes of TCNQ. Two-photon PES via a bound electronic excited state of TCNQ(-) at 3.100 eV yields a broad low kinetic energy peak due to fast internal conversion to vibrationally excited levels of the anion ground electronic state. The high EA measured for TCNQ underlies its ability as a good electron acceptor.

Communication: Observation of dipole-bound state and high-resolution photoelectron imaging of cold acetate anions.

We report the observation of a dipole-bound state and a high-resolution photoelectron imaging study of cryogenically cooled acetate anions (CH3COO(-)). Both high-resolution non-resonant and resonant photoelectron spectra via the dipole-bound state of CH3COO(-) are obtained. The binding energy of the dipole-bound state relative to the detachment threshold is determined to be 53 ± 8 cm(-1). The electron affinity of the CH3COO· neutral radical is measured accurately as 26 236 ± 8 cm(-1) (3.2528 ± 0.0010 eV) using high-resolution photoelectron imaging. This accurate electron affinity is validated by observation of autodetachment from two vibrational levels of the dipole-bound state of CH3COO(-). Excitation spectra to the dipole-bound states yield rotational profiles, allowing the rotational temperature of the trapped CH3COO(-) anions to be evaluated.

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.

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.

High-resolution photoelectron imaging and resonant photoelectron spectroscopy via noncovalently bound excited states of cryogenically cooled anions.

Valence-bound anions with polar neutral cores (µ > ∼2.5 D) can support dipole-bound excited states below the detachment threshold. These dipole-bound states (DBSs) are highly diffuse and the weakly bound electron in the DBS can be readily autodetached via vibronic coupling. Excited DBSs can be observed in photodetachment spectroscopy using a tunable laser. Tuning the detachment laser to above-threshold vibrational resonances yields vibrationally enhanced resonant photoelectron spectra, which are highly non-Franck-Condon with much richer vibrational information. This perspective describes recent advances in the studies of excited DBSs of cryogenically cooled anions using high-resolution photoelectron imaging (PEI) and resonant photoelectron spectroscopy (rPES). The basic features of dipole-bound excited states and highly non-Franck-Condon resonant photoelectron spectra will be discussed. The power of rPES to yield rich vibrational information beyond conventional PES will be highlighted, especially for low-frequency and Franck-Condon-inactive vibrational modes, which are otherwise not accessible from non-resonant conventional PES. Mode-selectivity and intra-molecular rescattering have been observed during the vibrationally induced autodetachment. Conformer-specific rPES is possible due to the different dipole-bound excited states of molecular conformers with polar neutral cores. For molecules with µ ≪ 2.5 D or without dipole moments, but large quadrupole moments, excited quadrupole-bound states can exist, which can also be used to conduct rPES.

Probing the Critical Dipole Moment To Support Excited Dipole-Bound States in Valence-Bound Anions.

We report photodetachment spectroscopy and high-resolution photoelectron imaging of para-halogen substituted phenoxide anions, p-XC6H4O- (X = F, Cl, Br, I). The dipole moments of the p-XC6H4O neutral radicals increase from 2.56 to 3.19 D for X = F to I, providing a series of similar molecules to allow the examination of charge-dipole interactions by minimizing molecule-dependent effects. Excited DBSs ([XC6H4O]*-) are observed for the four anions with binding energies of 8, 11, 24, and 53 cm-1, respectively, for X = F to I, below their respective detachment thresholds. The binding energies exhibit a linear correlation with the dipole moments of the neutral radicals, extrapolating to a critical dipole moment of 2.5 D for zero binding energy. Because of the small binding energy of the excited DBS of [FC6H4O]*-, rotational autodetachment is observed to compete with vibrational autodetachment in the resonant photoelectron spectra, resulting in electrons with near zero kinetic energies.

Resonant Two-Photon Photoelectron Imaging and Intersystem Crossing from Excited Dipole-Bound States of Cold Anions.

We report the observation of a dipole-bound state (DBS) 659 cm-1 below the electron detachment threshold of cryogenically cooled deprotonated 4,4'-biphenol anion (bPh-) and 19 of its lowest vibrational levels. Resonant two-photon photoelectron imaging (R2P-PEI) via the vibrational levels of the DBS displays a sharp peak with a constant binding energy. This observation indicates vertical detachment from the vibrational levels of the DBS to the corresponding neutral levels with the conservation of the vibrational energy, suggesting that the highly diffuse electron in the DBS has little effect on the neutral core. The R2P-PEI spectra also exhibit two features at lower binding energies, which come from intersystem crossings from the DBS to two lower-lying valence-bound triplet excited states of bPh-. The current study discloses the first R2P-PEI spectra from vibrational excited states of a DBS and direct spectroscopic evidence of transitions from a DBS to valence-bound states of anions.

Probing the interaction between the encapsulated water molecule and the fullerene cages in H2O@C60- and H2O@C59N.

We report a high-resolution photoelectron imaging study of cryogenically-cooled H2O@C60- and H2O@C59N- endohedral fullerene anions. The electron affinity (EA) of H2O@C60 is measured to be 2.6923 ± 0.0008 eV, which is 0.0088 eV higher than the EA of C60, while the EA of H2O@C59N is measured to be 3.0058 eV ± 0.0007 eV, which is 0.0092 eV lower than the EA of C59N. The opposite shifts are found to be due to the different electrostatic interactions between the encapsulated water molecule and the fullerene cages in the two systems. There is a net coulombic attraction between the guest and host in H2O@C60-, but a repulsive interaction in H2O@C59N-. We have also observed low-frequency features in the photoelectron spectra tentatively attributed to the hindered rotational excitations of the encapsulated H2O molecule, providing further insights into the guest-host interactions in H2O@C60- and H2O@C59N-.

High-Resolution Photoelectron Imaging of Cryogenically-Cooled C59N- and (C59N)22- Azafullerene Anions.

We report a photoelectron imaging study of cryogenically cooled C59N- and (C59N)22- anions produced from electrospray ionization. High-resolution photoelectron spectra are obtained for C59N- for the first time, allowing seven vibrational frequencies of the C59N azafullerene to be measured. The electron affinity of C59N is determined accurately to be 3.0150 ± 0.0007 eV. The observed vibrational features are understood on the basis of calculated frequencies and compared with those of C60 and C59HN. The photoelectron image of (C59N)22-, which has the same mass/charge ratio as C59N-, is also observed, allowing the second electron affinity of the (C59N)2 azafullerene dimer to be measured as 1.20 ± 0.05 eV. The intramolecular Coulomb repulsion of the (C59N)22- dianion is estimated to be 1.96 eV and is investigated theoretically using the electron density difference between (C59N)22- and (C59N)2.