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Functionalizing aromatic compounds with optical cycling centres

Nature Chemistry volume 14, pages 995–999 (2022)Cite this article

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Abstract

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.

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Fig. 1: 2D and DLIF spectra of CaO-Ph-3,4,5-F3.
Fig. 2: Vibrational decay ratios for all observed modes.
Fig. 3: pKa trends.

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Data availability

The experimental datasets and codes for Figs. 1–3 and Extended Data Fig. 1 are available as source data and from the online Zenodo repository at https://zenodo.org/record/6578610#.YsRnod8o9PY. Other data supporting the findings of this study are available in the Supplementary Information. Source data are provided with this paper.

References

  1. Campisciano, V., Gruttadauria, M. & Giacalone, F. Modified nanocarbons for catalysis. ChemCatChem 11, 90–133 (2019).

    Article  CAS  Google Scholar 

  2. Wang, Q. & Astruc, D. State of the art and prospects in metal-organic framework (MOF)-based and MOF derived nanocatalysis. Chem. Rev. 120, 1438–1511 (2020).

    Article  CAS  PubMed  Google Scholar 

  3. Liu, Y., Dong, X. & Chen, P. Biological and chemical sensors based on graphene materials. Chem. Soc. Rev. 41, 2283–2307 (2012).

    Article  CAS  PubMed  Google Scholar 

  4. Saha, K., Agasti, S. S., Kim, C., Li, X. & Rotello, V. M. Gold nanoparticles in chemical and biological sensing. Chem. Rev. 112, 2739–2779 (2012).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Guillemard, L., Kaplaneris, N., Ackermann, L. & Johansson, M. J. Late-stage C–H functionalization offers new opportunities in drug discovery. Nat. Rev. Chem. 5, 522–545 (2021).

    Article  CAS  Google Scholar 

  6. Di Rosa, M. Laser-cooling molecules. Eur. Phys. J. D 31, 395–402 (2004).

    Article  CAS  Google Scholar 

  7. Shuman, E. S., Barry, J. F. & DeMille, D. Laser cooling of a diatomic molecule. Nature 467, 820–823 (2010).

    Article  CAS  PubMed  Google Scholar 

  8. Anderegg, L. et al. Radio frequency magneto-optical trapping of CaF with high density. Phys. Rev. Lett. 119, 103201 (2017).

    Article  PubMed  Google Scholar 

  9. Isaev, T. A. & Berger, R. Polyatomic candidates for cooling of molecules with lasers from simple theoretical concepts. Phys. Rev. Lett. 116, 063006 (2016).

    Article  PubMed  CAS  Google Scholar 

  10. Vilas, N. B. et al. Magneto-optical trapping and subdoppler cooling of a polyatomic molecule. Nature 606, 70–74 (2022).

    Article  CAS  PubMed  Google Scholar 

  11. Kozyryev, I., Baum, L., Matsuda, K. & Doyle, J. Proposal for laser cooling of complex polyatomic molecules. Chem. Phys. Chem. 17, 3641–3648 (2016).

    Article  CAS  PubMed  Google Scholar 

  12. Mitra, D. et al. Direct laser cooling of a symmetric top molecule. Science 369, 1366–1369 (2020).

    Article  CAS  PubMed  Google Scholar 

  13. Ivanov, M. V., Bangerter, F. H. & Krylov, A. I. Towards a rational design of laser-coolable molecules: insights from equation-of-motion coupled-cluster calculations. Phys. Chem. Chem. Phys. 21, 19447–19457 (2019).

    Article  CAS  PubMed  Google Scholar 

  14. Ivanov, M. V., Bangerter, F. H., Wójcik, P. & Krylov, A. I. Toward ultracold organic chemistry: prospects of laser cooling large organic molecules. J. Phys. Chem. Lett. 11, 6670–6676 (2020).

    Article  CAS  PubMed  Google Scholar 

  15. Dickerson, C. E. et al. Franck-Condon tuning of optical cycling centers by organic functionalization. Phys. Rev. Lett. 126, 123002 (2021).

    Article  CAS  PubMed  Google Scholar 

  16. Dickerson, C. E. et al. Optical cycling functionalization of arenes. J. Phys. Chem. Lett. 12, 3989–3995 (2021).

    Article  CAS  PubMed  Google Scholar 

  17. Hutzler, N. R., Lu, H.-I. & Doyle, J. M. The buffer gas beam: an intense, cold, and slow source for atoms and molecules. Chem. Rev. 112, 4803–4827 (2012).

    Article  CAS  PubMed  Google Scholar 

  18. Domcke, W., Cederbaum, L., Köppel, H. & Von Niessen, W. A comparison of different approaches to the calculation of Franck-Condon factors for polyatomic molecules. Mol. Phys. 34, 1759–1770 (1977).

    Article  CAS  Google Scholar 

  19. Fischer, G. Vibronic Coupling: The Interaction Between the Electronic and Nuclear Motions (Academic, 1984).

  20. Paul, A. C. et al. Laser-induced fluorescence and dispersed-fluorescence spectroscopy of the \({\widetilde{A}}^{2}{E}-{\widetilde{X}}^{2}{A}_{1}\) transition of jet-cooled calcium methoxide (CaOCH3) radicals. J. Chem. Phys. 151, 134303 (2019).

    Article  PubMed  CAS  Google Scholar 

  21. Dagdigian, P. J. State-resolved collision-induced electronic transitions. Annu. Rev. Phys. Chem. 48, 95–123 (1997).

    Article  CAS  PubMed  Google Scholar 

  22. Hammett, L. P. The effect of structure upon the reactions of organic compounds. Benzene derivatives. J. Am. Chem. Soc. 59, 96–103 (1937).

    Article  CAS  Google Scholar 

  23. Mao, Y., Head-Gordon, M. & Shao, Y. Unraveling substituent effects on frontier orbitals of conjugated molecules using an absolutely localized molecular orbital based analysis. Chem. Sci. 9, 8598–8607 (2018).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  24. Liu, J. Rotational and fine structure of open-shell molecules in nearly degenerate electronic states. J. Chem. Phys. 148, 124112 (2018).

    Article  PubMed  CAS  Google Scholar 

  25. Augenbraun, B. L., Doyle, J. M., Zelevinsky, T. & Kozyryev, I. Molecular asymmetry and optical cycling: laser cooling asymmetric top molecules. Phys. Rev. X 10, 031022 (2020).

    CAS  Google Scholar 

  26. Baum, L. et al. Establishing a nearly closed cycling transition in a polyatomic molecule. Phys. Rev. A 103, 043111 (2021).

    Article  CAS  Google Scholar 

  27. Albert, V. V., Covey, J. P. & Preskill, J. Robust encoding of a qubit in a molecule. Phys. Rev. X 10, 031050 (2020).

    CAS  Google Scholar 

  28. Augenbraun, B. L. et al. Laser-cooled polyatomic molecules for improved electron electric dipole moment searches. New J. Phys. 22, 022003 (2020).

    Article  CAS  Google Scholar 

  29. Hutzler, N. R. Polyatomic molecules as quantum sensors for fundamental physics. Quantum Sci. Technol. 5, 044011 (2020).

    Article  Google Scholar 

  30. Blackmore, J. A. et al. Ultracold molecules for quantum simulation: rotational coherences in CaF and RbCs. Quantum Sci. Technol. 4, 014010 (2018).

    Article  Google Scholar 

  31. Yu, P., Cheuk, L. W., Kozyryev, I. & Doyle, J. M. A scalable quantum computing platform using symmetric-top molecules. New J. Phys. 21, 093049 (2019).

    Article  CAS  Google Scholar 

  32. Lane, I. C. Ultracold fluorine production via doppler cooled BeF. Phys. Chem. Chem. Phys. 14, 15078–15087 (2012).

    Article  CAS  PubMed  Google Scholar 

  33. Balakrishnan, N. Perspective: ultracold molecules and the dawn of cold controlled chemistry. J. Chem. Phys. 145, 150901 (2016).

    Article  CAS  PubMed  Google Scholar 

  34. Guo, H. et al. Surface chemical trapping of optical cycling centers. Phys. Chem. Chem. Phys. 23, 211–218 (2021).

    Article  CAS  PubMed  Google Scholar 

  35. Reilly, N. J., Schmidt, T. W. & Kable, S. H. Two-dimensional fluorescence (excitation/emission) spectroscopy as a probe of complex chemical environments. J. Phys. Chem. A 110, 12355–12359 (2006).

    Article  CAS  PubMed  Google Scholar 

  36. Gascooke, J. R., Alexander, U. N. & Lawrance, W. D. Two-dimensional laser induced fluorescence spectroscopy: a powerful technique for elucidating rovibronic structure in electronic transitions of polyatomic molecules. J. Chem. Phys. 134, 184301 (2011).

    Article  PubMed  CAS  Google Scholar 

  37. Kokkin, D. L., Steimle, T. C. & DeMille, D. Branching ratios and radiative lifetimes of the U, L and I states of thorium oxide. Phys. Rev. A 90, 062503 (2014).

    Article  CAS  Google Scholar 

  38. Augenbraun, B. L. et al. Observation and laser spectroscopy of ytterbium monomethoxide, YbOCH3. Phys. Rev. A 103, 022814 (2021).

    Article  CAS  Google Scholar 

  39. Perdew, J. P., Ernzerhof, M. & Burke, K. Rationale for mixing exact exchange with density functional approximations. J. Chem. Phys. 105, 9982–9985 (1996).

    Article  CAS  Google Scholar 

  40. Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).

    Article  PubMed  CAS  Google Scholar 

  41. Rappoport, D. & Furche, F. Property-optimized Gaussian basis sets for molecular response calculations. J. Chem. Phys. 133, 134105 (2010).

    Article  PubMed  CAS  Google Scholar 

  42. Frisch, M. J. et al. Gaussian 16, revision C.01 (Gaussian, 2016).

  43. Gozem, S. & Krylov, A. I. The ezSpectra Suite: an easy-to-use toolkit for spectroscopy modeling. Wiley Interdiscip. Rev. Comput. Mol. Sci 12, e1546 (2021).

    Google Scholar 

  44. Cheuk, L. W. et al. Λ-enhanced imaging of molecules in an optical trap. Phys. Rev. Lett. 121, 083201 (2018).

    Article  CAS  PubMed  Google Scholar 

  45. Zhang, C. et al. Accurate prediction and measurement of vibronic branching ratios for laser cooling linear polyatomic molecules. J. Chem. Phys. 155, 091101 (2021).

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

We thank T. C. Steimle for sharing critical equipment and for useful discussions and also N. Vilas and Y. Bao for helpful discussions. This work was supported in part by the National Science Foundation (grants nos. PHY-1255526, PHY-1415560, PHY-1912555, PHY-2110421, CHE-1900555, DGE-1650604, DGE-2034835 and OMA-2016245), the Army Research Office (grants nos. W911NF-15-1-0121, W911NF-14-1-0378, W911NF-13-1-0213, W911NF-17-1-0071 and W911NF-19-1-0297), AFOSR (grant no. FA9550- 20-1-0323) and the US Department of Energy, Office of Science, Basic Energy Sciences (award no. DE-SC0019245).

Author information

Author notes

  1. Debayan Mitra

    Present address: Department of Physics, Columbia University, New York, NY, USA

Authors and Affiliations

  1. Department of Physics and Astronomy, University of California, Los Angeles, CA, USA

    Guo-Zhu Zhu, Guanming Lao, Wesley C. Campbell & Eric R. Hudson

  2. Harvard-MIT Center for Ultracold Atoms, Cambridge, MA, USA

    Debayan Mitra, Benjamin L. Augenbraun, Zack D. Lasner & John M. Doyle

  3. Department of Physics, Harvard University, Cambridge, MA, USA

    Debayan Mitra, Benjamin L. Augenbraun, Michael J. Frim, Zack D. Lasner & John M. Doyle

  4. Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA

    Claire E. Dickerson, Anastassia N. Alexandrova & Justin R. Caram

  5. Center for Quantum Science and Engineering, University of California, Los Angeles, CA, USA

    Anastassia N. Alexandrova, Wesley C. Campbell, Justin R. Caram & Eric R. Hudson

  6. Challenge Institute for Quantum Computation, University of California, Los Angeles, CA, USA

    Wesley C. Campbell & Eric R. Hudson

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Contributions

A.N.A., W.C.C., J.R.C., J.M.D. and E.R.H. conceived the idea. D.M., B.L.A. and Z.D.L. constructed the vacuum, cryogenic and spectroscopic apparatus under the supervision of J.M.D. G.-Z.Z. and G.L. explored the initial production method. G.-Z.Z., D.M. and Z.D.L. acquired all the experimental data. C.E.D. performed all calculations. Z.D.L., D.M. and M.J.F. built the Pearson function to fit peaks in all DLIF spectra. G.-Z.Z. and D.M. analysed all data, with useful contributions from B.L.A., Z.D.L., W.C.C. and E.R.H. G.-Z.Z., D.M. and E.R.H. prepared the manuscript with contributions from all authors. The research was coordinated by W.C.C., J.M.D. and E.R.H.

Corresponding author

Correspondence to Eric R. Hudson.

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The authors declare no competing interests.

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Nature Chemistry thanks Jinjun Liu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 2D and DLIF spectra of all other five molecules.

a-c, CaO-Ph. d-f. CaO-Ph-3-CH3. g-i, CaO-Ph-3-F. j-l, CaO-Ph-3-CF3. m-n, CaO-Ph-3,4-F2. In the 2D spectra, the orange dashed lines mark features due to CaOH or CaF, while the green dotted lines indicate features from CaO-Ph-X species. In the corresponding dispersed LIF spectra, the experimental curves (black) are fitted with Pearson functions (red). The blue sticks illustrate the vibrational branching ratios of different vibrational modes. The assignments of resolved vibrational peaks are also given. The symbols * and + indicate features due to CaOH and Ca, respectively.

Source data

Supplementary information

Supplementary Information

Supplementary discussions of curve fitting and error analysis, Tables 1–11 and Figs. 1 and 2.

Source data

Source Data Fig. 1

Datasets of 1D and 2D spectra and Pearson fitting codes.

Source Data Fig. 2

Data and Matlab codes.

Source Data Fig. 3

Data of Fig.3 in excel.

Source Data Extended Data Fig. 1

Datasets of 1D and 2D spectra.

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Zhu, GZ., Mitra, D., Augenbraun, B.L. et al. Functionalizing aromatic compounds with optical cycling centres. Nat. Chem. 14, 995–999 (2022). https://doi.org/10.1038/s41557-022-00998-x

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