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arXiv:2411.03199

Bottom-up approach to scalable growth of molecules capable of optical cycling

Guanming Lao, Taras A. Khvorost, Jr. Macias, Harry W. T. Morgan, Robert H. Lavroff, Choi, Ryan, Haowen Zhou, Denis Usvyat, Guo‐Zhu Zhu, Miguel A. Garcı́a-Garibay, Anastassia N. Alexandrova, Eric R. Hudson, Wesley C. Campbell

Published Nov 5, 2024• 0 citations
arXivHTMLPDF

Abstract

Gas-phase molecules capable of repeatable, narrow-band spontaneous photon scattering are prized for direct laser cooling and quantum state detection. Recently, large molecules incorporating phenyl rings have been shown to exhibit similar vibrational closure to the small molecules demonstrated so far, and it is not yet known if the high vibrational-mode density of even larger species will eventually compromise optical cycling. Here, we systematically increase the size of hydrocarbon ligands attached to single alkaline-earth-phenoxides from (-H) to -C$_{14}$H$_{19}$ while measuring the vibrational branching fractions of the optical transition. We find that varying the ligand size from 1 to more than 30 atoms does not systematically reduce the cycle closure, which remains around 90%. Theoretical extensions to larger diamondoids and bulk diamond surface suggest that alkaline earth phenoxides may maintain the desirable scattering behavior as the system size grows further, with no indication of an upper limit.

DOI
10.48550/arxiv.2411.03199

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Gas-phase molecules capable of repeatable, narrow-band spontaneous photon scattering are prized for direct laser cooling and quantum state detection. Recently, large molecules incorporating phenyl rings have been shown to exhibit similar vibrational closure to the small molecules demonstrated so far, and it is not yet known if the high vibrational-mode density of even larger species will eventually compromise optical cycling. Here, we systematically increase the size of hydrocarbon ligands attached to single alkaline-earth-phenoxides from (-H) to -C14_{14}14​H19_{19}19​ while measuring the vibrational branching fractions of the optical transition. We find that varying the ligand size from 1 to more than 30 atoms does not systematically reduce the cycle closure, which remains around 90%. Theoretical extensions to larger diamondoids and bulk diamond surface suggest that alkaline earth phenoxides may maintain the desirable scattering behavior as the system size grows further, with no indication of an upper limit.
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.
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.
Rapid and repeated scattering of laser photons (``optical cycling'') underlies many uses of atoms and small molecules for quantum science and measurement. Larger polyatomic molecules are also appealing targets, partly because these species may be decorated with functional groups offering unique scientific opportunities. In this talk, we discuss a large class of aromatic molecules that can be functionalized with an alkaline-earth metal atom to enable optical cycling. We describe the gas-phase production of Ca- and Sr-bearing derivatives of phenyl (Ph) and naphthyl radicals and, using dispersed fluorescence spectroscopy, we show that these molecules contain multiple electronic transitions suitable for optical cycling and laser cooling. We present high-resolution laser excitation spectra for molecules such as fluorinated-CaOPh and SrOPh and compare these to the well-known alkaline-earth monoalkoxides and monoamides. These data inform ongoing work to laser cool and magneto-optically trap a functionalized aromatic molecule.
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.
Ultracold organic chemistry enables studies of reaction dynamics and mechanisms in the quantum regime. Access to ultracold molecules hinges on the ability to efficiently scatter multiple photons via quasi-closed cycling transitions. Optical cycling in polyatomic molecules is challenging due to their complex electronic structure. Using equation-of-motion coupled-cluster calculations, we demonstrate that an alkaline earth metal attached to various aromatic ligands (such as benzene, phenol, cyclopentadienyl, and pyrrolide) offers nearly closed cycling transitions with only a few additional repump lasers. We also show that aromatic ligands such as benzene can accommodate multiple cycling centers in various geometrical arrangements, opening new avenues in quantum information science, precision measurements, and ultracold chemistry.
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.