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Multivalent optical cycling centers: towards control of polyatomics with multi-electron degrees of freedom

Yu, Phelan and Lopez, Adrian and Goddard, William A., III and Hutzler, Nicholas R. (2023) Multivalent optical cycling centers: towards control of polyatomics with multi-electron degrees of freedom. Physical Chemistry Chemical Physics, 25 (1). pp. 154-170. ISSN 1463-9076. doi:10.1039/d2cp03545f.

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Optical control of polyatomic molecules promises new opportunities in precision metrology and fundamental chemistry, as well as quantum information and many-body science. Contemporary experimental and theoretical efforts have mostly focused on cycling photons via excitation of a single electron localized to an alkaline earth (group 2)-like metal center. In this paper, we consider pathways towards optical cycling in polyatomic molecules with multi-electron degrees of freedom, which arise from two or more cycling electrons localized to p-block post-transition metal and metalloid (group 13, 14, and 15) centers. We characterize the electronic structure and rovibrational branching of several prototypical candidates using ab initio 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.

Item Type:Article
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URLURL TypeDescription
Yu, Phelan0000-0002-3715-9133
Lopez, Adrian0000-0002-7915-2597
Goddard, William A., III0000-0003-0097-5716
Hutzler, Nicholas R.0000-0002-5203-3635
Additional Information:We thank Benjamin Augenbraun, Lan Cheng, Arian Jadbabaie, Anna Krylov, Nick Pilgram, and Paweł Wójcik for insightful discussions and input. We also thank the anonymous referees for thoughtful feedback, which greatly improved the presentation of our results. P. Y. acknowledges support from the Eddleman Graduate Fellowship through the Institute for Quantum Information and Matter (IQIM), the Gordon and Betty Moore Foundation (7947), and the Alfred P. Sloan Foundation (G-2019-12502). A. L. acknowledges support from the C. S. Shastry Prize and the Caltech Associates SURF Fellowship. W. A. G. was supported by the Ferkel Chair. N. R. H. acknowledges support from the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award No. DE-SC0019245. The computations presented here were conducted in the Resnick High Performance Computing Center, a facility supported by the Resnick Sustainability Institute at the California Institute of Technology.
Group:Institute for Quantum Information and Matter, Resnick Sustainability Institute
Funding AgencyGrant Number
Institute for Quantum Information and Matter (IQIM)UNSPECIFIED
Gordon and Betty Moore Foundation7947
Alfred P. Sloan FoundationG-2019-12502
C. S. Shastry PrizeUNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Department of Energy (DOE)DE-SC0019245
Resnick Sustainability InstituteUNSPECIFIED
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Issue or Number:1
Record Number:CaltechAUTHORS:20221216-550383000.6
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:118395
Deposited By: Research Services Depository
Deposited On:17 Dec 2022 15:15
Last Modified:27 May 2023 00:12

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