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Precise test of quantum electrodynamics and determination of fundamental constants with HD+ ions

Nature volume 581, pages 152–158 (2020)Cite this article

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Abstract

Bound three-body quantum systems are important for fundamental physics1,2 because they enable tests of quantum electrodynamics theory and provide access to the fundamental constants of atomic physics and to nuclear properties. Molecular hydrogen ions, the simplest molecules, are representative of this class3. The metastability of the vibration–rotation levels in their ground electronic states offers the potential for extremely high spectroscopic resolution. Consequently, these systems provide independent access to the Rydberg constant (R∞), the ratios of the electron mass to the proton mass (me/mp) and of the electron mass to the deuteron mass (me/md), the proton and deuteron nuclear radii, and high-level tests of quantum electrodynamics4. Conventional spectroscopy techniques for molecular ions5,6,7,8,9,10,11,12,13,14 have long been unable to provide precision competitive with that of ab initio theory, which has greatly improved in recent years15. Here we improve our rotational spectroscopy technique for a sympathetically cooled cluster of molecular ions stored in a linear radiofrequency trap16 by nearly two orders in accuracy. We measured a set of hyperfine components of the fundamental rotational transition. An evaluation resulted in the most accurate test of a quantum-three-body prediction so far, at the level of 5 × 10−11, limited by the current uncertainties of the fundamental constants. We determined the value of the fundamental constants combinations \({R}_{\infty }{m}_{{\rm{e}}}({m}_{{\rm{p}}}^{-1}+{m}_{{\rm{d}}}^{-1})\) and mp/me with a fractional uncertainty of 2 × 10−11, in agreement with, but more precise than, current Committee on Data for Science and Technology values. These results also provide strong evidence of the correctness of previous key high-precision measurements and a more than 20-fold stronger bound for a hypothetical fifth force between a proton and a deuteron.

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Fig. 1: Energy diagram of the spin structures and favoured transitions.
Fig. 2: Hyperfine components of the fundamental rotational transition of HD+ at 1.3 THz.
Fig. 3: Exclusion plot (95% confidence limit) for a Yukawa-type interaction between a proton and a deuteron, deduced from spectroscopy of MHIs.
Fig. 4: Comparison of results of this work with literature values.

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Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

References

  1. Karshenboim, S. G. (ed.) Precision Physics of Simple Atoms and Molecules (Springer-Verlag, 2008).

  2. Pachucki, K., Patkóš, V. & Yerokhin, V. A. Testing fundamental interactions on the helium atom. Phys. Rev. A 95, 062510 (2017).

    ADS  Google Scholar 

  3. Leach, C. A. & Moss, R. E. Spectroscopy and quantum mechanics of the hydrogen molecular cation: a test of molecular quantum mechanics. Annu. Rev. Phys. Chem. 46, 55–82 (1995).

    ADS  CAS  PubMed  Google Scholar 

  4. Roth, B. et al. in Precision Physics of Simple Atoms and Molecules (ed. Karshenboim, S. G.) 205–232 (Springer-Verlag, 2008).

  5. Wing, W. H., Ruff, G. A., Lamb, W. E. & Spezeski, J. J. Observation of the infrared spectrum of the hydrogen molecular ion HD+. Phys. Rev. Lett. 36, 1488–1491 (1976).

    ADS  CAS  Google Scholar 

  6. Arcuni, P. W., Fu, Z. W. & Lundeen, S. R. Energy difference between the (ν = 0, R = 1) and the (ν = 0, R = 3) states of \({{\rm{H}}}_{2}^{+}\), measured with interseries microwave spectroscopy of H2 Rydberg states. Phys. Rev. A 42, 6950–6953 (1990).

    ADS  CAS  PubMed  Google Scholar 

  7. Carrington, A., McNab, I. R., Montgomerie-Leach, C. A. & Kennedy, R. A. Vibration-rotation spectroscopy of the HD+ ion near the dissociation limit. Mol. Phys. 72, 735–762 (1991).

    ADS  CAS  Google Scholar 

  8. Fu, Z. W., Hessels, E. A. & Lundeen, S. R. Determination of the hyperfine structure of \({{\rm{H}}}_{2}^{+}\) (ν = 0, R = 1) by microwave spectroscopy of high-L, n = 27 Rydberg states of H2. Phys. Rev. A 46, R5313–R5316 (1992).

    ADS  CAS  PubMed  Google Scholar 

  9. Critchley, A. D. J., Hughes, A. N. & McNab, I. R. Direct measurement of a pure rotation transition in \({{\rm{H}}}_{2}^{+}\). Phys. Rev. Lett. 86, 1725–1728 (2001).

    ADS  CAS  PubMed  Google Scholar 

  10. Osterwalder, A., Wüest, A., Merkt, F. & Jungen, C. High-resolution millimeter wave spectroscopy and multichannel quantum defect theory of the hyperfine structure in high Rydberg states of molecular hydrogen \({{\rm{H}}}_{2}^{+}\). J. Chem. Phys. 121, 11810–11838 (2004).

    ADS  CAS  PubMed  Google Scholar 

  11. Koelemeij, J. C. J., Roth, B., Wicht, A., Ernsting, I. & Schiller, S. Vibrational spectroscopy of HD+ with 2-ppb accuracy. Phys. Rev. Lett. 98, 173002 (2007).

    ADS  Google Scholar 

  12. Bressel, U. et al. Manipulation of individual hyperfine states in cold trapped molecular ions and application to HD+ frequency metrology. Phys. Rev. Lett. 108, 183003 (2012).

    ADS  CAS  PubMed  Google Scholar 

  13. Haase, C., Beyer, M., Jungen, C. & Merkt, F. The fundamental rotational interval of para-\({{\rm{H}}}_{2}^{+}\) by MQDT-assisted Rydberg spectroscopy of H2. J. Chem. Phys. 142, 064310 (2015).

    ADS  PubMed  Google Scholar 

  14. Biesheuvel, J. et al. Probing QED and fundamental constants through laser spectroscopy of vibrational transitions in HD+. Nat. Commun. 7, 10385 (2016).

    ADS  CAS  PubMed  PubMed Central  Google Scholar 

  15. Korobov, V. I., Hilico, L. & Karr, J.-P. Fundamental transitions and ionization energies of the hydrogen molecular ions with few ppt uncertainty. Phys. Rev. Lett. 118, 233001 (2017).

    ADS  PubMed  Google Scholar 

  16. Alighanbari, S., Hansen, M. G., Korobov, V. I. & Schiller, S. Rotational spectroscopy of cold and trapped molecular ions in the Lamb–Dicke regime. Nat. Phys. 14, 555–559 (2018).

    CAS  Google Scholar 

  17. Jefferts, K. B. Hyperfine structure in the molecular ion \({{\rm{H}}}_{2}^{+}\). Phys. Rev. Lett. 23, 1476–1478 (1969).

    ADS  CAS  Google Scholar 

  18. Schiller, S. & Korobov, V. I. Test of time-dependence of the electron and nuclear masses with ultracold molecules. Phys. Rev. A 71, 032505 (2005).

    ADS  Google Scholar 

  19. Bakalov, D. & Schiller, S. The electric quadrupole moment of molecular hydrogen ions and their potential for a molecular ion clock. Appl. Phys. B 114, 213–230 (2014); erratum 116, 777–778 (2014).

    ADS  CAS  Google Scholar 

  20. Karr, J.-Ph. \({{\rm{H}}}_{2}^{+}\) and HD+: candidates for a molecular clock. J. Mol. Spectrosc. 300, 37–43 (2014).

    ADS  CAS  Google Scholar 

  21. Schiller, S., Bakalov, D. & Korobov, V. I. Simplest molecules as candidates for precise optical clocks. Phys. Rev. Lett. 113, 023004 (2014).

    ADS  CAS  PubMed  Google Scholar 

  22. Beyer, A. et al. The Rydberg constant and proton size from atomic hydrogen. Science 358, 79–85 (2017).

    ADS  MathSciNet  CAS  PubMed  MATH  Google Scholar 

  23. Fleurbaey, H. et al. New measurement of the 1S−3S transition frequency of hydrogen: contribution to the proton charge radius puzzle. Phys. Rev. Lett. 120, 183001 (2018).

    ADS  CAS  PubMed  Google Scholar 

  24. Bezginov, N. et al. A measurement of the atomic hydrogen Lamb shift and the proton charge radius. Science 365, 1007–1012 (2019).

    ADS  CAS  PubMed  Google Scholar 

  25. Antognini, A. et al. Proton structure from the measurement of 2S–2P transition frequencies of muonic hydrogen. Science 339, 417–420 (2013).

    ADS  CAS  PubMed  Google Scholar 

  26. Grémaud, B., Delande, D. & Billy, N. Highly accurate calculation of the energy levels of the \({{\rm{H}}}_{2}^{+}\) molecular ion. J. Phys. B 31, 383 (1998).

    ADS  Google Scholar 

  27. Moss, R. E. Energies of low-lying vibration-rotation levels of \({{\rm{H}}}_{2}^{+}\) and its isotopomers. J. Phys. B 32, L89–L91 (1999).

    ADS  CAS  Google Scholar 

  28. Taylor, J. M., Yan, Z.-C., Dalgarno, A. & Babb, J. F. Variational calculations on the hydrogen molecular ion. Mol. Phys. 97, 25–33 (1999).

    ADS  CAS  Google Scholar 

  29. Tiesinga, E., Mohr, P. J., Newell, D. B. & Taylor, B. N. Values of fundamental physical constants. NIST https://physics.nist.gov/cuu/Constants/index.html (2019).

  30. Wolf, F. et al. Non-destructive state detection for quantum logic spectroscopy of molecular ions. Nature 530, 457–460 (2016).

    ADS  CAS  PubMed  Google Scholar 

  31. Chou, C. et al. Preparation and coherent manipulation of pure quantum states of a single molecular ion. Nature 545, 203–207 (2017).

    ADS  CAS  PubMed  Google Scholar 

  32. Schneider, T., Roth, B., Duncker, H., Ernsting, I. & Schiller, S. All-optical preparation of molecular ions in the rovibrational ground state. Nat. Phys. 6, 275–278 (2010).

    CAS  Google Scholar 

  33. Roth, B., Blythe, P., Wenz, H., Daerr, H. & Schiller, S. Ion-neutral chemical reactions between ultracold localized ions and neutral molecules with single-particle resolution. Phys. Rev. A 73, 042712 (2006).

    ADS  Google Scholar 

  34. Schiller, S., Roth, B., Lewen, F., Ricken, O. & Wiedner, M. Ultra-narrow-linewidth continuous-wave THz sources based on multiplier chains. Appl. Phys. B 95, 55–61 (2009).

    ADS  CAS  Google Scholar 

  35. Bakalov, D., Korobov, V. I. & Schiller, S. High-precision calculation of the hyperfine structure of the HD+ ion. Phys. Rev. Lett. 97, 243001 (2006).

    ADS  PubMed  Google Scholar 

  36. Schiller, S. & Korobov, V. I. Canceling spin-dependent contributions and systematic shifts in precision spectroscopy of molecular hydrogen ions. Phys. Rev. A 98, 022511 (2018).

    ADS  CAS  Google Scholar 

  37. Bakalov, D., Korobov, V. I. & Schiller, S. Magnetic field effects in the transitions of the HD+ molecular ion and precision spectroscopy. J. Phys. B 44, 025003 (2011); corrigendum 45, 049501 (2012).

    ADS  Google Scholar 

  38. Korobov, V. I., Koelemeij, J. C. J., Hilico, L. & Karr, J.-P. Theoretical hyperfine structure of the molecular hydrogen ion at the 1 ppm level. Phys. Rev. Lett. 116, 053003 (2016).

    ADS  PubMed  Google Scholar 

  39. Menasian, S. C. & Dehmelt, H. G. High-resolution study of (1,1/2,1/2)−(1,1/2,3/2) HFS transition in \({{\rm{H}}}_{2}^{+}\). Bull. Am. Phys. Soc. 18, 408 (1973).

    Google Scholar 

  40. Heiße, F. et al. High-precision mass spectrometer for light ions. Phys. Rev. A 100, 022518 (2019).

    ADS  Google Scholar 

  41. Fink, D. J. & Myers, E. G. Deuteron-to-proton mass ratio from the cyclotron frequency ratio of \({{\rm{H}}}_{2}^{+}\) to D+ with \({{\rm{H}}}_{2}^{+}\) in a resolved vibrational state. Phys. Rev. Lett. 124, 013001 (2020).

    ADS  CAS  PubMed  Google Scholar 

  42. Sturm, S. et al. High-precision measurement of the atomic mass of the electron. Nature 506, 467–470 (2014).

    ADS  CAS  PubMed  Google Scholar 

  43. Pastor, P. C. et al. Absolute frequency measurements of the 23S 1 → 23P 0,1,2 atomic helium transitions around 1083 nm. Phys. Rev. Lett. 92, 023001 (2004).

    ADS  PubMed  Google Scholar 

  44. Hori, M. et al. Buffer-gas cooling of antiprotonic helium to 1.5 to 1.7 K, and antiproton-to-electron mass ratio. Science 354, 610–614 (2016).

    ADS  CAS  PubMed  Google Scholar 

  45. Rengelink, R. J. et al. Precision spectroscopy of helium in a magic wavelength optical dipole trap. Nat. Phys. 14, 1132–1137 (2018).

    CAS  Google Scholar 

  46. Hori, M. et al. Two-photon laser spectroscopy of antiprotonic helium and the antiproton-to-electron mass ratio. Nature 475, 484–488 (2011).

    CAS  PubMed  Google Scholar 

  47. Udem, T. Quantum electrodynamics and the proton size. Nat. Phys. 14, 632–632 (2018); correction 14, 767 (2018).

    CAS  Google Scholar 

  48. Schiller, S., Bakalov, D., Bekbaev, A. K. & Korobov, V. I. Static and dynamic polarizability and the Stark and blackbody-radiation frequency shifts of the molecular hydrogen ions \({{\rm{H}}}_{2}^{+}\), HD+, and \({{\rm{D}}}_{2}^{+}\). Phys. Rev. A 89, 052521 (2014).

    ADS  Google Scholar 

  49. Berkeland, D. J., Miller, J. D., Bergquist, J. C., Itano, W. M. & Wineland, D. J. Minimization of ion micromotion in Paul trap. J. Appl. Phys. 83, 5025–5033 (1998).

    ADS  CAS  Google Scholar 

  50. Shen, J., Borodin, A. & Schiller, S. A simple method for characterization of the magnetic field in an ion trap using Be+ ions. Eur. Phys. J. D 68, 359 (2014).

    ADS  Google Scholar 

  51. Bakalov, D. & Schiller, S. The electric quadrupole moment of molecular hydrogen ions and their potential for a molecular ion clock. Appl. Phys. B 114, 213–230 (2014); corrigendum 116, 777–778 (2014).

    ADS  CAS  Google Scholar 

  52. Salumbides, E. J., Ubachs, W. & Korobov, V. I. Bounds on fifth forces at the sub-Å length scale. J. Mol. Spectrosc. 300, 65–69 (2014).

    ADS  CAS  Google Scholar 

  53. Pavanello, M., Tung, W.-C. & Adamowicz, L. Determination of deuteron quadrupole moment from calculations of the electric field gradient in D2 and HD. Phys. Rev. A 81, 042526 (2010).

    ADS  Google Scholar 

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Acknowledgements

We thank M. G. Hansen for assistance with optimization of the apparatus and J.-Ph. Karr for checking theoretical expressions. This work has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement number 786306, ‘PREMOL’), and from the Deutsche Forschungsgemeinschaft in project Schi 431/23-1. S.A. acknowledges a fellowship of the Prof.-W.-Behmenburg-Schenkung. V.I.K. acknowledges support from the Russian Science Foundation under grant number 18-12-00128.

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Authors and Affiliations

  1. Institut für Experimentalphysik, Heinrich-Heine-Universität Düsseldorf, Düsseldorf, Germany

    S. Alighanbari, G. S. Giri, F. L. Constantin & S. Schiller

  2. Laboratoire PhLAM CNRS UMR 8523, Université Lille 1, Villeneuve d’Ascq, France

    F. L. Constantin

  3. Bogoliubov Laboratory of Theoretical Physics, Joint Institute for Nuclear Research, Dubna, Russia

    V. I. Korobov

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Contributions

S.A. and G.S.G. performed the measurements and analysed data, F.L.C. contributed to the measurements. S.A. developed and maintained the apparatus. V.I.K. performed the ab initio calculations, S.S. performed data and theoretical analyses, prepared the manuscript and supervised the work. All authors contributed to discussion and manuscript editing.

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Correspondence to S. Schiller.

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Peer review information Nature thanks Brian Odom, Richard Thompson and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data figures and tables

Extended Data Fig. 1 Conceptual view of the arrangement used for high-resolution spectroscopy of HD+ using TICTES.

The spectroscopy wave (1.3 THz) crosses the ion cluster perpendicular to its long axis, enabling spectroscopy in the Lamb–Dicke regime. The ion cluster comprises atomic Be+ ions (blue dots) and HD+ molecular ions (red dots). The indicated laser beams implement the Doppler cooling of Be+ ions (313 nm), rotational cooling of HD+ (2.7 µm and 5.48 μm) and detection by REMPD (266 nm and 1.4 μm). The magnetic field B lifts the degeneracy of Zeeman sublevels during terahertz spectroscopy. The polarizer and the half-wave plate enable adjustment of the polarization and intensity of the terahertz radiation.

Extended Data Fig. 2 Beryllium ion fluorescence during one preparation–spectroscopy cycle.

Spectroscopy (terahertz wave on) occurs during the interval marked ‘REMPD’. Beryllium laser cooling is on all the time. SE, secular excitation. B, a magnetic flux strength B is applied during REMPD. B0, a strength B0 is applied for rotational laser cooling. CPS, counts per second. The signal obtained from the spectroscopy cycle is indicated in cyan.

Extended Data Fig. 3 Systematic shifts of the Zeeman component 19+ of the rotational hyperfine transition line 19.

a, The trap’s amplitude is decreased by 2.5 V from \({V}_{{\rm{RF}}}^{(1)}\) to \({V}_{{\rm{RF}}}^{(2)}\). The FWHM linewidth is 4 Hz, corresponding to 3 × 10−12 fractional FWHM. b, The light shift induced by the 266 nm and 1.4 μm dissociation lasers, determined by comparing two spectroscopy modes. ‘Continuous’ indicates that the lasers are on when the terahertz radiation is applied. ‘Interleaved’ indicates that the lasers and terahertz radiation are on alternatingly.

Extended Data Table 1 Spin Hamiltonian coefficients, spin-structure frequencies and spin-frequency derivatives
Full size table

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Alighanbari, S., Giri, G.S., Constantin, F.L. et al. Precise test of quantum electrodynamics and determination of fundamental constants with HD+ ions. Nature 581, 152–158 (2020). https://doi.org/10.1038/s41586-020-2261-5

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