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The Journal of Physical Chemistry Letters

Zwitterions Functionalized by Optical Cycling Centers: Toward Laser-Coolable Polyatomic Molecular Cations

Hryhory Sinenka, Yurii Bruyakin, Andrei V. Zaitsevskii, Timur A. Isaev, Anastasia V. Bochenkova

Published Jun 16, 2023• 3 citations
Publisher

Abstract

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.

DOI
10.1021/acs.jpclett.3c00904

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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.
Molecules with optical cycling centers (OCCs) are highly desirable in the context of fundamental studies as well as applications (e.g., quantum computing) because they can be effectively cooled to very low temperatures by repeated absorption and emission (hence, cycling). Charged species offer additional advantages for experimental control and manipulation. We present a systematic computational study of a series of diatomic radical-cations made of a d-block metal and a p-block ligand, that are isoelectronic (in their valence shell) to the successfully laser-cooled neutral molecules. Using high-level electronic structure methods, we characterize state and transition properties of low-lying electronic states and compute Franck-Condon factors. The computed branching ratios and radiative lifetimes reveal that the electronic transitions analogous to those successfully used in the laser cooling of neutral molecules are less than optimal in the cations. We propose alternative transitions suitable for optical cycling and highlight trends that could assist future designs of OCCs in charged or neutral molecules.
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.
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.
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.
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.
A novel molecular structure that bridges the fields of molecular optical cycling and molecular photoswitching is presented. It is based on a photoswitching molecule azobenzene functionalized with one and two CaO- groups, which can act as optical cycling centers (OCCs). This paper characterizes the electronic structure of the resulting model systems, focusing on three questions: (1) how the electronic states of the photoswitch are impacted by a functionalization with an OCC; (2) how the states of the OCC are impacted by the scaffold of the photoswitch; and (3) whether the OCC can serve as a spectroscopic probe of isomerization. The experimental feasibility of the proposed design and the advantages that organic synthesis can offer in the further functionalization of this molecular scaffold are also discussed. This work brings into the field of molecular optical cycling a new dimension of chemical complexity intrinsic to only polyatomic molecules.