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The Journal of Physical Chemistry Letters

Toward Ultracold Organic Chemistry: Prospects of Laser Cooling Large Organic Molecules

Maxim V. Ivanov, Felix H. Bangerter, Paweł Wójcik, Anna I. Krylov

Published Jul 27, 2020• 42 citations
Publisher

Abstract

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.

DOI
10.1021/acs.jpclett.0c01960

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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.
Molecules cooled to ultracold temperatures are desirable for applications in fundamental physics and quantum information science. However, cooling polyatomic molecules with more than six atoms has not yet been achieved. Building on the idea of an optical cycling center (OCC), a moiety supporting a set of localized and isolated electronic states within a polyatomic molecule, molecules with two OCCs (bi-OCCs) may afford better cooling efficiency by doubling the photon scattering rate. By using quantum chemistry calculations, we assess the extent of the coupling of the two OCCs with each other and the molecular scaffold. We show that promising coolable bi-OCC molecules can be proposed by following chemical design principles.
Functionalization of large aromatic compounds and biomolecules with optical cycling centers (OCC) is of considerable interest for the design and engineering of molecules with a highly selective optical photoresponse. Both internal and external dynamics in such molecules can be precisely controlled by lasers, enabling their efficient cooling and opening up broad prospects for high-precision spectroscopy, ultracold chemistry, enantiomer separation, and various other fields. The way the OCC is bonded to a molecular ligand is crucial to the optical properties of the OCC, first of all, for the degree of closure of the optical cycling loop. Here we introduce a novel type of functionalized molecular cation where a positively charged OCC is bonded to various organic zwitterions with a particularly high permanent dipole moment. We consider strontium(I) complexes with betaine and other zwitterionic ligands and show the possibility of creating efficient and highly closed population cycling for dipole-allowed optical transitions in such complexes.
quantum chemical methods. Despite increased internal complexity and challenging design parameters, we find several molecules possessing quasi-closed photon cycling schemes with highly diagonal, visible and near-infrared transitions. Furthermore, we identify new heuristics for engineering optically controllable and laser-coolable polyatomic molecules with multi-electron cycling centers. Our results help elucidate the interplay between hybridization, repulsion, and ionicity in optically active species and provide new directions for using polyatomic molecules with complex electronic structure as a resource for quantum science and measurement.