Sub-part-per-trillion test of the Standard Model with atomic hydrogen

Abstract

Quantum electrodynamics (QED), the first relativistic quantum field theory, describes light–matter interactions at a fundamental level and is one of the pillars of the Standard Model (SM). Through the extraordinary precision of QED, the SM predicts the energy levels of simple systems such as the hydrogen atom with up to 13 significant digits¹, making hydrogen spectroscopy an ideal test bed. The consistency of physical constants extracted from different transitions in hydrogen using QED, such as the proton charge radius r_p, constitutes a test of the theory. However, values of r_p from recent measurements^2,3,4,5,6,7 of atomic hydrogen are partly discrepant with each other and with a more precise value from spectroscopy of muonic hydrogen^8,9. This prevents a test of QED at the level of experimental uncertainties. Here we present a measurement of the 2S–6P transition in atomic hydrogen with sufficient precision to distinguish between the discrepant values of r_p and enable rigorous testing of QED and the SM overall. Our result ν_2S–6P = 730,690,248,610.79(48) kHz gives a value of r_p = 0.8406(15) fm at least 2.5-fold more precise than from other atomic hydrogen determinations and in excellent agreement with the muonic value. The SM prediction of the transition frequency (730,690,248,610.79(23) kHz) is in excellent agreement with our result, testing the SM to 0.7 parts per trillion (ppt) and, specifically, bound-state QED corrections to 0.5 parts per million (ppm), their most precise test so far.

Main

The binding energy of atomic hydrogen can be expressed as¹

$${E}_{{nlJ}}=ch{R}_{{\infty }}\left({f}_{{nJ}}^{\mathrm{Dirac}}(\alpha ,\frac{{m}_{{\rm{p}}}}{{m}_{{\rm{e}}}})+{f}_{{nlJ}}^{\mathrm{QED}}(\alpha ,\frac{{m}_{{\rm{p}}}}{{m}_{{\rm{e}}}},\ldots )+{\delta }_{l0}\frac{{C}_{\mathrm{NS}}}{{n}^{3}}{r}_{{\rm{p}}}^{2}\right),$$

(1)

in which n, l and J are, respectively, the principal, orbital and total electronic angular momentum quantum numbers of the energy level of interest. ${f}_{{nJ}}^{{\rm{Dirac}}}$ is the Dirac eigenvalue (∝1/n² in leading order), whereas the second term ${f}_{{nlJ}}^{{\rm{QED}}}$ (∝1/n³ in leading order) contains the corrections from bound-state QED, such as self-energy and vacuum polarization, including muonic and hadronic contributions¹. Both terms depend on the fine-structure constant α and the electron-to-proton mass ratio m_p/m_e, which are known with sufficient accuracy from other experiments that do not require bound-state QED (refs. ^{1,10,11,12,13,14}). The third term is the leading-order nuclear size correction for S-states (l = 0), accounting for the finite root-mean-square (rms) charge radius of the proton, r_p. The second and third terms constitute the Lamb shift and contribute about 1 ppm and 100 ppt, respectively, to the 2S–6P transition frequency (Extended Data Table 1). The unitless terms are converted to SI units (International System of Units) using the Rydberg constant R_∞.

To compare measured energy levels or transition frequencies with equation (1), r_p and R_∞ must be known (speed of light in vacuum c and Planck’s constant h are defined). In practice, r_p and R_∞ are largely determined from such measurements themselves and more than two measurements of distinct transitions are necessary to test equation (1).

A special case is the determination of r_p with laser spectroscopy of muonic hydrogen^8,9,15. In this exotic atom, the electron is replaced with a negative muon, whose larger mass increases C_NS of equation (1) by four orders of magnitude, allowing a precise determination of r_p without requiring other high-precision input. Because the nuclear size correction scales as 1/n³ as the other QED corrections, discrepant r_p values from atomic and muonic hydrogen can indicate missing or incomplete QED terms (Methods). Notably, the value of r_p from the muonic measurement was found to be significantly smaller (>5σ) than the then-established value (CODATA 2014 (ref. ¹⁶)).

This proton radius puzzle led to extensive research efforts^{2,3,4,5,6,7,17}. We first addressed it with a precision measurement of the 2S–4P transition in atomic hydrogen², which favoured the muonic result, but could not conclusively (>5σ) rule out the previous value. Subsequent measurements in atomic hydrogen have followed^3,4,5,6,7 but they are partly discrepant with the muonic value and with each other, and none is precise enough to conclusively test the muonic value, as visualized in Fig. 1. Until now, this has prevented a verification of QED at the level of experimental uncertainties.

Fig. 1: Proton rms charge radius r_p.

Previous determinations of r_p from atomic hydrogen spectroscopy (refs. ^2,3,4,5,6,7; black circles) are partly discrepant with each other and with the value of r_p from spectroscopy of muonic hydrogen (refs. ^8,9,15; violet square) and therefore could not conclusively resolve the initial 5.6σ discrepancy between the 2010 muonic value and the then-established larger value (as summarized in the CODATA 2014 global adjustment of fundamental constants¹⁶; brown hexagon). The value of r_p from atomic hydrogen spectroscopy of the 2S–6P transition in this work (blue bar and diamond) is at least 2.5-fold more precise than other atomic hydrogen determinations and in excellent agreement with the muonic value. It disagrees with the fourfold less precise CODATA 2014 value by 5.5σ. The r_p values are determined by combining each measurement with the 1S–2S transition frequency¹⁸ and equation (1) (Pearson correlation coefficient r < 0.05 between r_p values). The most recent CODATA 2022 global adjustment (ref. ¹; green triangle) essentially corresponds to the muonic value owing to the exceptionally low uncertainty of the latter. Error bars show one-standard-deviation uncertainties. Electron–proton scattering data are not shown, as different analyses give significantly different values of r_p (refs. ^1,48). Lattice QCD calculations of r_p show promise but are not yet competitive⁴⁹. See Extended Data Fig. 2 for the Rydberg constant R_∞ from atomic hydrogen combined with the muonic value of r_p.

Source data

Here we report on laser spectroscopy of the 2S–6P transition in atomic hydrogen with sufficient precision to distinguish between the discrepant values of r_p. This precision corresponds to finding the transition frequency to one part in 15,000 of the experimental linewidth, to our knowledge unprecedented for laser spectroscopy, requiring a thorough understanding of any asymmetric distortions of the line shape at that level and a large experimental signal-to-noise ratio. By combining our measurement with the precisely known 1S–2S transition frequency¹⁸, we determine r_p with 2.5-fold higher precision than the previous best determination from atomic hydrogen⁵ (Fig. 1). Our value of r_p is in excellent agreement with the muonic value but fourfold more precise than and in significant disagreement (5.5σ) with the CODATA 2014 value¹⁶. Consequently, we use the muonic value of r_p as input to equation (1) (along with the 1S–2S transition frequency), which allows us to compare the SM prediction of the 2S–6P transition frequency with our measurement. This constitutes a test of the SM to 0.7 ppt and of bound-state QED corrections to 0.5 ppm.

Principle of the measurement

2S–6P transition

We study the 2S–6P transition in a cryogenic beam of hydrogen atoms using Doppler-free one-photon laser spectroscopy. Although the transition has been previously observed with laser spectroscopy^19,20, this work presents a substantial improvement. Using a linearly polarized, 410-nm spectroscopy laser, we alternately examine two dipole-allowed transitions from the metastable initial ${2{\rm{S}}}_{1/2}^{F=0},{m}_{F}=0$ level: the 2S–6P_1/2 transition to the ${6{\rm{P}}}_{1/2}^{F=1},{m}_{F}=0$ level and the 2S–6P_3/2 transition to the ${6{\rm{P}}}_{3/2}^{F=1},{m}_{F}=0$ level, as shown in Fig. 2a (F, total angular momentum quantum number; m_F, magnetic quantum number). The excited 6P levels rapidly decay, directly or through cascades, to the 1S and 2S manifolds, resulting in a Γ = 3.90 MHz natural transition linewidth. These decays, predominantly the direct Lyman-ε decay to the 1S manifold, are the experimental signal and the fluorescence line shape is observed in line scans by recording this signal at different spectroscopy laser detunings. A fraction of γ_ei/Γ = 3.9% or 7.9% of decays from the excited level lead back to the initial 2S level for the 2S–6P_1/2 or 2S–6P_3/2 transitions, respectively. Notably, quantum interference (QI) between excitation–decay paths that go through either excited level but lead to the same final level can cause substantial distortions of the fluorescence line shape. The associated line shifts are on the order of Γ²/Δν_FS(6P) ≈ Γ/100 (refs. ^2,21,22), in which Δν_FS(6P) ≈ 405 MHz is the 6P fine-structure splitting between the excited levels. Because the magnitude and sign of the distortions depend on the detection direction (relative to the laser polarization), here we use a large detection solid angle and a magic polarization angle to strongly suppress the shift²².

Fig. 2: Doppler-free one-photon spectroscopy of the 2S–6P transition.

a, Relevant level scheme of atomic hydrogen (not to scale). Solid arrows indicate laser-driven transitions and dashed arrows indicate spontaneous decay. Spectroscopy laser is on resonance with 2S–6P_1/2 (dark blue) or 2S–6P_3/2 (light blue) transitions. Levels shown in grey are not resonantly coupled by lasers. b, Key components of experimental apparatus (to scale, cutaway). Dashed black lines (orthogonal to spectroscopy laser) visualize atomic beam offset angle α₀ (exaggerated) and laser polarization angle θ_L. c, Typical line scan of the 2S–6P_1/2 transition (acquired within 40 s; full detuning range is ±50 MHz; Methods). The fluorescence signal (top detector; kcts, kilocounts) is recorded for different velocity groups τ_i with mean speeds $\bar{v}$, with three shown here (orange, green and purple circles; τ₁₆ scaled (×3) for visibility). Error bars show expected one-standard-deviation (σ) shot noise. The FWHM linewidth Γ_F reduces for slower velocity groups as Doppler broadening reduces. Solid lines show simulated line shape (scaled and offset to match the signal) and the dotted orange line shows the Voigt line shape fit to τ₂ (see Extended Data Fig. 1 for fit residuals). P_2S–6P = 10 μW spectroscopy laser power and α₀ = 0 mrad were used. d, Resonance frequencies ν₀ (circles) determined from Voigt line shape fits to velocity groups of scan of panel c versus $\bar{v}$. Error bars show 1σ fit uncertainty. Extrapolation to zero speed (blue line; blue shading, 1σ confidence interval) gives Doppler-free transition frequency ν_e and Doppler slope κ. ν₀ has been corrected for light force, QI and second-order Doppler shifts and all other corrections. e, Histogram of all 598 detector-averaged Doppler-free transition frequencies ν_e (data group G3 of Extended Data Table 3) determined with the same experimental parameters as the line scan of panels c and d.

Source data

Experimental apparatus

The key in-vacuum components of the experimental apparatus (described in detail in ref. ²³) are shown in Fig. 2b. Briefly, a cryogenic beam of hydrogen atoms is formed by a copper nozzle (circular aperture with r₁ = 1 mm radius) held at temperature T_N = 4.8 K. The atoms are prepared in the initial ${2{\rm{S}}}_{1/2}^{F=0},{m}_{F}=0$ level by Doppler-free two-photon excitation from the 1S ground level with a preparation laser (243 nm wavelength; Fig. 2a,b), collinear with the atomic beam. The divergence of the atomic beam is limited to approximately 10 mrad in the transverse (x) direction by a collimating aperture (1.2 mm width, placed 154 mm after the nozzle).

The atomic beam enters the 2S–6P spectroscopy region inside a cylindrical detector assembly, in which, at a distance L = 204 mm from the nozzle, it crosses counterpropagating (along x) spectroscopy laser beams at an adjustable atomic beam offset angle |α₀| = 0–12 mrad from the orthogonal. In the ideal case of laser beams with identical wavefront curvature and power, this excitation scheme produces a line shape whose centre of mass is free of first-order Doppler shifts (but not necessarily free of Doppler broadening), as the interaction with the respective beams results in Doppler shifts of equal magnitude but opposite sign. Here an active fibre-based retroreflector (AFR)^24,25,26, consisting of polarization-maintaining fibre, collimator and high-reflectivity mirror, generates the required high-quality, wavefront-retracing beams (2.2 mm 1/e² intensity radius; P_2S–6P = 5–30 μW power in each beam). The AFR is attached to the rotatable detector cylinder, allowing an in situ adjustment of α₀ (1 mrad accuracy). We align α₀ close to zero to avoid splitting the line shape into two Doppler components from the counterpropagating beams, except when characterizing the light force shift (LFS; see below). The polarization angle θ_L of the laser beams, relative to the axis of the cylinder (along y), is set to 56.5°, the magic angle at which QI distortions are suppressed, or orthogonal to it (146.5°).

The photons emitted by the 6P decay eject photoelectrons from the cylinder walls, which are drawn to and counted with channel electron multipliers at the top and bottom of the cylinder (top and bottom detectors). Each detector covers >20% of the total solid angle, further suppressing QI distortions. A segmented Faraday cage surrounds the spectroscopy region, shielding external electric fields and allowing the application of bias fields to characterize stray electric fields and the dc-Stark shift caused by such fields (Methods).

Doppler-free one-photon spectroscopy

We investigate different atomic velocity groups τ_i (i = 1–16; Extended Data Table 2) by periodically blocking the 1S–2S preparation laser, thereby intermittently stopping the production of 2S atoms, and recording the signal as a function of delay time τ = 10–2,560 μs. The longer the τ, the slower the 2S atoms contributing to the signal. The speed distribution of atoms contributing to the signal is well described by a Maxwell–Boltzmann flux distribution with an extra multiplicative factor exp(−v_cut-off/v) with a characteristic cut-off speed v_cut-off ≈ 50 m s⁻¹, accounting for the loss of slower atoms through collisions (Methods). The mean speeds $\bar{v}$ of the velocity groups cover a wide range (253(5) to 65(1) m s⁻¹; overall mean speed $\langle \bar{v}\rangle =195(6)\,{\rm{m}}{{\rm{s}}}^{-1}$) and their transverse velocities are approximately Gaussian distributed with a full width at half maximum (FWHM) ranging from 3.4 to 0.6 m s⁻¹ (parentheses give the standard deviation over the data groups of Extended Data Table 3).

Figure 2c shows the top detector signal for three velocity groups (circles) for a typical line scan of the 2S–6P_1/2 transition. Fast velocity groups, such as τ₂ (orange circles), have a FWHM linewidth Γ_F substantially larger than the natural linewidth Γ, owing to Doppler broadening from their large transverse velocity widths. Conversely, for slower velocity groups (green and purple circles), Γ_F approaches Γ as the transverse velocity width decreases. Overall, Γ_F ranges from 9.6(4) to 5.5(6) MHz (Extended Data Table 2).

Our line shape simulations (solid lines; here the QI model is shown; Methods) are in excellent agreement with the experimental data, reproducing the Doppler broadening with v_cut-off as the only free parameter. The resonance frequency ν₀ of each velocity group is determined by fitting simple Voigt or Voigt doublet line shapes (dotted line; Methods) to the data. This differs from the approach taken in our previous 2S–4P measurement², in which a theoretically motivated, asymmetric line shape model was used to account for QI distortions. Here the QI distortions are much smaller, owing to the magic polarization angle and large detection solid angle, and distortions from the LFS dominate (Extended Data Fig. 1), for which no equivalent line shape model is known to us. Instead, we fit the same simple line shape model to the simulations and correct the experimental resonance frequency with our LFS and QI simulations.

To remove any residual first-order Doppler shift, we use the linear model ${\nu }_{0}={\nu }_{{\rm{e}}}+\kappa \bar{v}$ to extrapolate the resonance frequencies ν₀ of each line scan to zero speed (Fig. 2d). This gives the Doppler-free transition frequency ν_e, the Doppler slope κ and the resulting effective frequency correction $\Delta {\nu }_{{\rm{e}}}=-\kappa \langle \bar{v}\rangle$ (Methods). Figure 2e shows ν_e of all 598 line scans recorded with the same experimental parameters as in Fig. 2c,d. In total, the dataset presented here contains 3,155 line scans, acquired in three measurement runs (A, B and C) and grouped into 17 experimental parameter combinations (data groups; Extended Data Table 3).

Light force shift

Just as light waves diffract on a periodic structure, matter waves can diffract on the periodic structure formed by a standing wave of light, as first predicted for electrons by Kapitza and Dirac²⁷. Here a similar diffraction can occur as the atoms, which may be understood as matter waves, cross the standing intensity wave formed by the counterpropagating spectroscopy laser beams used to suppress the first-order Doppler shift (Fig. 2b). This effect, along with scattering on the standing wave, leads to a distortion of the fluorescence line shape and a line shift (LFS). Although such shifts have been observed in other experiments using standing waves^28,29,30, the behaviour and size of the shift and the necessary theoretical treatment are highly dependent on the exact experimental conditions. A travelling wave can be used to avoid the LFS³¹ but this approach has not yet demonstrated the level of Doppler shift suppression required here.

Diffraction of matter waves, as for light waves, requires some degree of spatial coherence, with diffraction becoming important when the atoms’ transverse coherence length l_c,t along the standing wave is comparable with its periodicity of λ/2 = 205 nm. Treating the cryogenic nozzle as a thermal source of atoms, we find l_c,t to be λ_dB,th = 0.8 nm (ref. ³²) and therefore much smaller than λ/2, in which ${\lambda }_{{\rm{dB}},{\rm{th}}}=\sqrt{{h}^{2}{k}_{{\rm{B}}}{T}_{{\rm{N}}}/2{\rm{\pi }}{m}_{{\rm{H}}}}$ is the thermal de Broglie wavelength (m_H, hydrogen mass; k_B, Boltzmann constant). However, as is well known from the van Cittert–Zernike theorem³³, the transverse coherence length is enhanced by propagation, as seen in matter wave interference of large molecules from a thermal source³⁴. At a distance L from the nozzle, this results in

$${l}_{{\rm{c}},{\rm{t}}}\approx (L/{r}_{1}){\lambda }_{{\rm{dB}}}/{\rm{\pi }}$$

(2)

for atoms with a speed v and de Broglie wavelength of λ_dB = h/m_Hv. For v = 200 m s⁻¹, the mean speed of atoms examined in the experiment, l_c,t is 129 nm at the standing wave and hence comparable with its periodicity. We therefore need to model the atoms as partially coherent matter waves, that is, the atoms are partially delocalized over the standing wave, unlike the localized description³⁵ valid for different experimental conditions^28,29.

We use the Wigner function³⁶ to find a quantum-mechanical description of the atomic beam, quantizing the motion along the standing wave while treating other directions classically. This results in a comparable value of l_c,t as estimated above²³. The interaction of the atoms with the standing wave can be described in the combined basis of internal energy levels and external momenta along the standing wave (Supplementary Methods). The absorption of a photon from the forward-travelling (+) or backward-travelling (−) beam excites atoms from the 2S to the 6P level and changes their momentum along the beams by ±ħK_L (wavenumber K_L = 2π/λ; ħ = h/2π). Likewise, stimulated emission into either beam returns atoms to the 2S level and changes their momentum by ∓ħK_L. This corresponds to a change in velocity by the recoil velocity, v_rec = ħK_L/m_H ≈ 0.97 m s⁻¹, comparable with the typical transverse velocity v_x of the atoms. Because the 6P level predominantly spontaneously decays to the 1S ground level, from which there is no re-excitation while the signal is recorded, the maximum relevant momentum change is here ±4ħk.

The small fraction γ_ei/Γ of the spontaneous decays back to the initial 2S level leads to a random momentum change along the direction of the standing wave, as the direction of the emitted photon is randomly distributed³⁷. The associated Doppler shift of such a decay (at most twice the recoil shift of Δν_rec = 1,176.03 kHz) is below the natural linewidth Γ and therefore the atom can be re-excited to the 6P level and ultimately contribute to the signal. However, because γ_ei/Γ ≪ 1, only at most one such back decay is relevant here.

We first simulate the interaction of the atoms with the standing wave for an atom initially in a momentum eigenstate, that is, as a fully delocalized matter wave, with transverse velocity v_x ≈ v(δα + α₀). Figure 3a shows the LFS ν_LFS, found with a Voigt line shape fit to the simulated line shape, for an atom with v = 200 m s⁻¹ (note that ν_LFS is always symmetric in v_x). The hypothetical situation without back decay to the 2S level (dotted black line) describes pure diffraction of the matter wave on the standing wave. At v_x = v_rec, the Bragg condition is met and the atoms coherently scatter photons between the two counterpropagating beams, resulting in a narrow resonance with shifts exceeding 200 kHz (Fig. 3b). Below this resonance, the shift is negative and approximately constant around zero v_x, and above the resonance, the shift is positive and tends to zero as v_x increases. Allowing back decay, on the other hand, allows scattering of the atoms on the standing wave. This primarily leads to a positive shift above the resonance that approximately scales with γ_ei/Γ, as shown for the 2S–6P_1/2 (γ_ei/Γ = 3.9%; blue solid line) and 2S–6P_3/2 (γ_ei/Γ = 7.9%; dashed red line) transitions.

Fig. 3: Simulation and measurement of LFS.

a, Simulation of LFS ν_LFS, resulting from interaction of atoms with the standing intensity wave (periodicity λ/2 = 205 nm) formed by counterpropagating spectroscopy laser beams. The simulation describes the atoms as delocalized over nodes and antinodes, crossing the standing wave with speed v = 200 m s⁻¹ and at angle δα + α₀ to orthogonal (transverse velocity of v_x ≈ v(δα + α₀); Fig. 2b). Results are shown for 2S–6P_1/2 (solid blue line) and 2S–6P_3/2 (dashed red line) transitions (at equal Rabi frequency), for which, respectively, 3.9% and 7.9% of the 6P level decays lead back to the 2S level (Fig. 2a). The hypothetical situation without back decay is also shown (dotted black line). At v_x = v_rec ≈ 0.97 m s⁻¹ (the recoil velocity), a Bragg resonance occurs, leading to a large shift. The shift is symmetric in v_x and negative (positive) for |v_x| ≲ v_rec (|v_x| ≳ v_rec). The simulated distribution (smoothed and scaled for visibility) of v_x for an atomic beam offset angle α₀ of 0 mrad (12 mrad) is indicated at the top (bottom) for velocity groups τ₂, τ₁₃ and τ₁₆ (arbitrary vertical units). b, Detail of the Bragg resonance. c, Similar to Fig. 2c but for a line scan with α₀ = 12 mrad, which splits the line into two Doppler components. The line is fitted with Voigt doublet line shape (Methods). d, Doppler-free transition frequency ν_e (blue circles) of the 2S–6P_1/2 transition for data taken at P_2S–6P = 30 μW and |α₀| = 0, 7.5 and 12 mrad and corrected for all systematic effects except LFS. The simulation of LFS (orange circles) is in excellent agreement with the experimental data. Error bars show combined statistical and systematic uncertainty (experimental data) or uncertainty from input parameters (simulation).

Source data

The partially coherent atomic beam corresponds to an incoherent sum over atoms in various momentum eigenstates (Supplementary Methods). Because the transverse velocity spread of the beam is on the order of v_rec (see shaded area at the top of Fig. 3a showing the velocity distribution of selected velocity groups and Extended Data Table 2), this prevents us from experimentally resolving the Bragg resonance and partly averages out the shift (to at most −0.96 kHz and −1.28 kHz for the 2S–6P_1/2 and 2S–6P_3/2 transitions, respectively, both occurring for velocity group τ₁₃).

To test our model and simulation of the LFS, we measured the transition frequency of the 2S–6P_1/2 transition at atomic beam offset angles of α₀ = ±7.5 mrad and α₀ = ±12 mrad, as well as the dataset with α₀ = 0 mrad (Fig. 3c,d). In particular, we find the difference in Doppler-free transition frequency between the data taken at α₀ = ± 12 mrad and α₀ = 0 mrad (both for P_2S–6P = 30 μW), having applied a correction of 0.17(28) kHz for all systematic effects except the LFS, to be

$${\nu }_{{\rm{e}}}^{(\text{no LFS corr.})}(\pm 12\,{\rm{mrad}})-{\nu }_{{\rm{e}}}^{(\text{no LFS corr.})}(0\,{\rm{mrad}})=4.32(1.83)\,{\rm{kHz}}.$$

(3)

The uncertainty is dominated by the statistical uncertainty of 1.63 kHz of the ±12 mrad data. This difference is in excellent agreement with the LFS simulation, which predicts ν_e,LFS(±12 mrad) − ν_e,LFS(0 mrad) = 4.21(61) kHz. The accompanying distortion of the experimental line shape, clearly observable in the asymmetry of fit residuals (Extended Data Fig. 1), is distinctly different for the two values of α₀ and in excellent agreement with the simulations. The measured LFS at α₀ = ±7.5 mrad is also in agreement with the simulation but has a comparatively large statistical uncertainty of 3.04 kHz (Fig. 3d). This comparison is also a powerful test of the Doppler shift suppression scheme (equation (3) includes a Doppler shift correction of Δν_e = −1.92(1.81) kHz) because of the large difference in α₀ and of the data analysis because of the qualitatively different line shapes involved.

Quantum interference

We use the QI simulations developed and extensively tested in ref. ² to estimate any remaining QI shift, which we find to be −0.25(36) kHz and 0.05(15) kHz for the 2S–6P_1/2 and 2S–6P_3/2 transitions, respectively (Methods). These values include a small subset of data taken orthogonal to the magic angle, at which QI distortions are larger, to test our simulations. Also, we make use of the fact that the distortions are of opposite sign (and different magnitude) for the two transitions²² and combine the 2S–6P_1/2 and 2S–6P_3/2 transition frequencies with a 1:2 ratio into the 2S–6P fine-structure centroid (Methods). This reduces the shift to only −0.05(2) kHz.

2S–6P transition frequencies

By averaging all available data (Fig. 4), we find the transition frequencies of the 2S–6P_1/2 transition (ν_1/2) and the 2S–6P_3/2 transition (ν_3/2) to be

$${\nu }_{1/2}={\mathrm{730,690,111,486.30}(49)}_{{\rm{stat}}}{(49)}_{{\rm{sys}}}\,{\rm{kHz}}=\mathrm{730,690,111,486.30}(69)\,{\rm{kHz}}\,[0.94\,{\rm{ppt}}],$$

(4)

$${\nu }_{3/2}={\mathrm{730,690,516,650.91}(60)}_{{\rm{stat}}}{(28)}_{{\rm{sys}}}\,{\rm{kHz}}=\mathrm{730,690,516,650.91}(66)\,{\rm{kHz}}\,[0.90\,{\rm{ppt}}].$$

(5)

The final one-standard-deviation uncertainties (σ) are the combined statistical (‘stat’) and systematic (‘sys’) uncertainties, with the former corresponding to the Doppler shift extrapolation uncertainty. All corrections and uncertainties are listed in Extended Data Table 4, with contributions not discussed in the main text detailed in Methods and Supplementary Methods. The results from the two detectors, averaged here, agree within their uncertainties. The average Doppler slopes $\bar{\kappa }$ of both transitions are compatible with zero.

Fig. 4: Transition frequencies and Doppler slopes for the two examined 2S–6P transitions.

a, Measured transition frequencies ν_e of the 2S–6P_1/2 transition for different data groups (that is, combinations of experimental parameters and measurement runs), as labelled below each data point and listed in Extended Data Table 3. Data were taken for various combinations of spectroscopy laser power (10, 20 and 30 μW), atomic beam offset angle α₀ (α₀ = 0 mrad unless stated otherwise) and laser polarization angle θ_L (magic angle θ_L = 56.5° by default; non-magic angle θ_L = 146.5° marked accordingly). The data were collected over several months in 3-week-long runs, run A (circles), run B (diamonds) and run C (squares). Error bars show combined statistical and systematic one-standard-deviation (σ) uncertainty and the purple-shaded area shows the weighted mean of all data and its 1σ uncertainty. Black markers show the results without experiment-specific corrections, including for the light force, QI and first-order and second-order Doppler shifts (Extended Data Table 4). b, Doppler slopes κ for the data groups of panel a, determined in situ using velocity-resolved detection (Fig. 2). The mean speed of the atomic beam is $\langle \bar{v}\rangle \approx 195\,{\rm{m}}\,{{\rm{s}}}^{-1}$. $\bar{\kappa }$ is the weighted mean Doppler slope. c,d, Same as panels a and b but for the 2S–6P_3/2 transition. Spectroscopy laser powers have a 2:1 ratio for the 2S–6P_1/2 and 2S–6P_3/2 transitions to keep their Rabi frequencies identical. The Pearson correlation coefficient between ν_e and κ is r = −0.78 over all data groups.

Source data

By taking the difference of the two measured transition frequencies, we find the 6P fine-structure splitting between the ${6{\rm{P}}}_{1/2}^{F=1}$ and ${6{\rm{P}}}_{3/2}^{F=1}$ levels,

$$\Delta {\nu }_{{\rm{FS}}}(6{\rm{P}})={\nu }_{3/2}-{\nu }_{1/2}=\mathrm{405,164.62}(97)\,{\rm{kHz}}.$$

(6)

Extended Data Table 4 lists the corrections and uncertainties. The QED prediction Δν_FS,QED(6P) = 405,164.51(1) kHz (Methods), which at our level of accuracy does not depend on r_p, is in excellent agreement (Δν_FS(6P) − Δν_FS,QED(6P) = 0.11(97) kHz). This comparison tests the (uncorrelated) Doppler shift extrapolation and corrections for the light force, QI and dc-Stark shifts, with the last two of opposite sign for the two transitions.

Finally, we combine the two transition frequencies into the 2S–6P fine-structure centroid,

$${\nu }_{2{\rm{S}}-6{\rm{P}}}=\frac{1}{3}{\nu }_{1/2}+\frac{2}{3}{\nu }_{3/2}+\Delta {\nu }_{{\rm{HFS}}}({\nu }_{2{\rm{S}}-6{\rm{P}}})$$

(7)

$${\nu }_{2{\rm{S}}-6{\rm{P}}}=\mathrm{730,690,248,610.79}(48)\,{\rm{kHz}}\,[0.66\,{\rm{ppt}}],$$

(8)

with the hyperfine-structure (HFS) correction Δν_HFS(ν_2S–6P) = −132,985.25(1) kHz (Methods). The corrections and uncertainties for ν_2S–6P are listed in Table 1. The total applied correction, excluding the precisely known recoil shift and HFS corrections, corresponds to 3.6σ, with the largest individual correction (for the LFS) corresponding to 2.4σ. The relative uncertainty corresponds to a sixfold improvement over our previous 2S–4P measurement².

Table 1 Corrections Δν and uncertainties σ for the determination of the 2S–6P fine-structure centroid ν_2S–6P

R _∞ and r _p from atomic hydrogen

Combining the 2S–6P fine-structure centroid ν_2S–6P of equation (8) with a measurement of the 1S–2S transition frequency¹⁸, and using equation (1), we determine the proton rms charge radius as

$${r}_{{\rm{p}}}=0.8406{(5)}_{{\rm{QED}}}{(14)}_{\exp }\,{\rm{fm}}=0.8406(15)\,{\rm{fm}}.$$

(9)

The total uncertainty arises mostly from the uncertainty of ν_2S–6P (‘exp’), with the QED uncertainty of equation (1) (‘QED’) approximately threefold lower (contributions from the 1S–2S transition frequency and other physical constants are negligible). Figure 1 shows equation (9) with other relevant determinations of r_p. Equation (9) is the most precise value for r_p from any measurement other than the muonic measurement^9,15, being 2.5-fold and sixfold more precise than the next best determination from atomic hydrogen⁵ and our 2S–4P measurement², respectively. Equation (9) is in excellent agreement with the muonic measurement¹⁵ (r_p = 0.84060(39) fm) but disagrees with the CODATA 2014 proton radius¹⁶ by 5.5σ. Instead of r_p, we may also determine the 1S Lamb shift as ${{\mathcal{L}}}_{\exp }(1{\rm{S}})\,=\,{\mathrm{8,172,744.13}(14)}_{{\rm{Q}}{\rm{E}}{\rm{D}}}{(3.56)}_{\exp }\,{\rm{k}}{\rm{H}}{\rm{z}}\,=$ $\mathrm{8,172,744.1}(3.6)\,{\rm{kHz}}$ (Methods).

The Rydberg constant can be similarly extracted from the combination of the 1S–2S and 2S–6P transition frequencies, giving R_∞ = 10,973,731.568152(14) m⁻¹ (1.3 ppt; Pearson correlation coefficient r = 0.94 with equation (9)). However, because the theory predictions of both frequencies depend on R_∞ and r_p, we cannot make full use of the relative precision of 0.66 ppt of ν_2S–6P.

Test of the SM prediction

Having confirmed the muonic value of r_p, we now explicitly compare the SM prediction ν_2S–6P,SM for the 2S–6P fine-structure centroid with the experimentally determined value ν_2S–6P. Combining the 1S–2S transition frequency¹⁸ and the muonic value of r_p (ref. ¹⁵) with equation (1) (Methods), we find

$${\nu }_{2{\rm{S}}-6{\rm{P}},{\rm{SM}}}={\mathrm{730,690,248,610.79}(18)}_{{\rm{QED}}}{(14)}_{{r}_{{\rm{p}}}}\,{\rm{kHz}}=\mathrm{730,690,248,610.79}(23)\,{\rm{kHz}}\,[0.31\,{\rm{ppt}}].$$

(10)

The prediction is in excellent agreement with our experimental result with a difference of ν_2S–6P − ν_2S–6P,SM = 0.00(53) kHz, corresponding to a test of the SM at a relative precision of 0.7 ppt. This precision is comparable with the test of the SM prediction of the electron magnetic moment, which is at present limited to 0.7 ppt by discrepant measurements of α (ref. ¹²). Likewise, we compare the 1S Lamb shift prediction ${{\mathcal{L}}}_{{\rm{QED}}}(1{\rm{S}})\,=\,{\mathrm{8,172,744.1}(1.3)}_{{\rm{QED}}}{(1.0)}_{{{\rm{r}}}_{{\rm{p}}}}\,{\rm{kHz}}\,=\,\mathrm{8,172,744.1}(1.7)\,{\rm{kHz}}$ with ${{\mathcal{L}}}_{\exp }(1{\rm{S}})$, which, to our knowledge, is the most precise test (0.5 ppm) of bound-state QED corrections so far.

Extended Data Table 1 lists the QED corrections and their uncertainties. Our experimental uncertainty is comparable with the muonic and hadronic vacuum polarization corrections and reaches the level of three-photon corrections (∝α⁵), matching the highest-order terms in the prediction of the electron magnetic moment¹². Although the experimental uncertainty is 2.7-fold larger than the QED uncertainty (dominated by two-photon and radiative-recoil corrections), the latter is partly estimated by the expected size of uncalculated terms^1,38 as opposed to experimental tests. In fact, a recent recalculation of the two-photon self-energy³⁹ would shift ${{\mathcal{L}}}_{{\rm{QED}}}(1{\rm{S}})$ on the order of the experimental σ of ${{\mathcal{L}}}_{\exp }(1{\rm{S}})$.

Equivalently, we can compare the values of R_∞ determined from ν_2S–6P or the 1S–2S transition frequency, each in combination with the muonic value of r_p and equation (1). For ν_2S–6P, this gives

$${R}_{\infty }={\mathrm{10,973,731.5681524}(25)}_{{\rm{Q}}{\rm{E}}{\rm{D}}}{(72)}_{\exp }{(19)}_{{r}_{{\rm{p}}}}\,{{\rm{m}}}^{-1}=\mathrm{10,973,731.5681524}(79)\,{{\rm{m}}}^{-1}\,[0.75\,{\rm{p}}{\rm{p}}{\rm{t}}],$$

(11)

with the uncertainty limited by the precision of ν_2S–6P. Using the 1S–2S transition frequency yields a compatible R_∞ = 10,973,731.5681523(65) m⁻¹ (r_1S–2S = 0.40 correlation with equation (11)), limited by the uncertainty of ${{\mathcal{L}}}_{{\rm{QED}}}(1{\rm{S}})$. Equation (11) is compatible with and 50% more precise than the R_∞ world average¹, which has an expanded uncertainty accounting for scatter in the input data. Adding the 2S–6P measurement will probably reduce scatter in future adjustments as less precise measurements are removed. This situation is illustrated in Extended Data Fig. 2. Our measurement can also be used to improve new physics constraints on weakly interacting bosons with masses in the keV range^40,41.

The techniques demonstrated here may be used with any 2S–nP transitions in atomic hydrogen and deuterium⁴², with a precision matching or exceeding that of SM predictions feasible. Together with complementary approaches^{43,44,45,46,47}, we expect this to substantially advance bound-state QED tests.

Methods

Data acquisition

Here we give further relevant details on the experimental scheme and apparatus (both described in detail in ref. ²³). The run time of the cryogenic atomic beam is limited to freezing cycles of approximately 2 h by the accumulation of frozen (molecular) hydrogen inside the nozzle, which is removed by heating the nozzle to room temperature. The vacuum (2 × 10⁻⁷ mbar, dominated by molecular hydrogen) inside the 2S–6P spectroscopy region is maintained by differential pumping with a cryopump to minimize pressure shifts^50,51,52, with the temperature of the apparatus allowed to equilibrate on each measurement day before collecting data.

The power of the linearly polarized, 243-nm 1S–2S preparation laser^53,54 is resonantly enhanced in an in-vacuum, standing-wave cavity to P_1S–2S ≈ 1 W per direction (297 μm 1/e² intensity waist radius). The observed 1S–2S transition linewidth is approximately 3 kHz (FWHM; atomic detuning, as opposed to laser detuning), limited by single-photon ionization of the 2S level⁵⁵. Therefore, the ${2{\rm{S}}}_{1/2}^{F=1}$ levels are only populated by Doppler-sensitive two-photon excitation, leading to a population of approximately 7 × 10⁻⁷ in each sublevel relative to the population in the ${2{\rm{S}}}_{1/2}^{F=0}$ level. The detuning of the preparation laser is set several times per freezing cycle by observing the 1S–2S transition. An equal-slit-width optical chopper running at 160 Hz periodically blocks the preparation laser (which sets delay time τ = 0 μs) to enable the velocity-resolved detection. The channel electron multipliers are switched off with a fast high-voltage switch while the preparation laser is unblocked to prevent saturation from scattered 243-nm light.

By using a linearly polarized 2S–6P spectroscopy laser^53,54 and the ${2{\rm{S}}}_{1/2}^{F=0}$ level as the initial level, only transitions to the ${6{\rm{P}}}_{1/2}^{F=1}$ hyperfine level (2S–6P_1/2 transition) and the ${6{\rm{P}}}_{3/2}^{F=1}$ hyperfine level (2S–6P_3/2 transition) are dipole-allowed, whereas the excitation of the ${6{\rm{P}}}_{1/2}^{F=0}$ and ${6{\rm{P}}}_{3/2}^{F=2}$ levels is prevented by angular momentum conservation (Fig. 2a). The line strengths (∝μ², in which μ is the dipole moment) of the 2S–6P_1/2 and 2S–6P_3/2 transitions have a 1:2 ratio. We use spectroscopy laser powers P_2S–6P with a ratio of 2:1 for the two transitions to keep their Rabi frequencies ${\varOmega }_{0}\propto \mu \sqrt{{P}_{2{\rm{S}}-6{\rm{P}}}}$ identical (the peak Rabi frequency is (2π × 126) krad s⁻¹ at our highest spectroscopy laser powers of 30 and 15 μW, respectively). Most 6P decays (branching ratio Γ_e–1S/Γ = 88.2%) are Lyman decays to the 1S manifold, with the most energetic, direct Lyman-ε decay (Γ_det/Γ = 80.5%) dominating, whereas the remaining γ_e–2S/Γ = 11.8% are Balmer decays to the 2S manifold, of which in turn a fraction γ_ei/Γ leads back to the initial ${2{\rm{S}}}_{1/2}^{F=0}$ level (see Section 1.2 in the Supplementary Methods). The metastable 2S levels are treated as stable here, as their natural lifetime (122 ms) is much longer than the time the atoms spend in the atomic beam (see Section 2.6 in the Supplementary Methods for the 2S decay contribution to the signal background).

The channel electron multipliers count the fluorescence photons from the 6P decays, either by detecting the photoelectrons emitted by the photons from the detector cylinder walls or, to a lesser extent, directly detecting the photons. Because the photoelectron yield strongly increases with photon energy (for both colloidal graphite and oxidized aluminium, the surface materials of the Faraday cage and the detector cylinder, respectively), fluorescence from Lyman-ε decay (13.2 eV photon energy) constitutes approximately 97% of the signal detected by the channel electron multipliers. The counts are binned into the 16 velocity groups by their delay time τ, with the bins chosen to cover a wide range of mean speeds $\overline{v}$ while exhibiting a sufficient signal-to-noise ratio (bin width 50–550 μs; Extended Data Table 2). For each line scan, we accumulate counts over 160 chopper cycles at each spectroscopy laser detuning. Intermittently, excess scatter and spiking was observed for the bottom detector and its signal was subsequently discarded (≈11% of line scans; Extended Data Table 3). We attribute this to the bottom detector being cooled down to close to, and possibly below, its lower operating temperature limit because of its vicinity to the cryopump.

At least once per measurement day, the nozzle and the collimating aperture are centred on the preparation laser. At the start of each freezing cycle, the atomic beam offset angle α₀, which is controlled by a linear motor equipped with a position sensor, is aligned to zero with a 1 mrad alignment uncertainty. This is achieved by blocking the returning beam of the spectroscopy laser (using an in-vacuum shutter in front of the high-reflectivity mirror of the AFR^25,26), determining the (now unsuppressed) Doppler slope κ for several angles and moving to the angle at which κ is zero, which is set as α₀ = 0 mrad. To record line scans at a non-zero angle ±α₀, we first move to either +α₀ or −α₀ (chosen randomly) and then to the opposite sign, recording typically 5–10 scans at each angle, and repeating this procedure several times per freezing cycle. The fibre–collimator distance of the AFR is optimized^25,26 at least once per freezing cycle.

We use fixed sets of 30 symmetric (15 unique) detunings Δ of the spectroscopy laser frequency to sample the 2S–6P fluorescence line shape, with different sets used for α₀ = 0, ±7.5 and ±12 mrad to account for the different line shapes (see Section 5.1.3 and Table 5.2 of ref. ²³), all of which have ±50 MHz as the largest detuning. The detunings were chosen to minimize the statistical uncertainty of the Doppler-free transition frequency ν_e, whereas the number of detunings and the acquisition time (1 s) at each detuning were chosen to balance between sufficient line sampling, signal-to-noise ratio and number of line scans per freezing cycle. For each line scan, the order of the detunings is randomized to minimize the influence of drifts in the signal. At the beginning of each freezing cycle, the centre laser frequency (to which the detunings are added) was chosen randomly from a normal distribution. This distribution was centred on the 2S–6P transition frequency expected from the muonic measurement of the proton radius⁹, with a standard deviation of 12 kHz to cover the transition frequency expected from the CODATA 2014 value of the proton radius¹⁶. The laser frequencies are referenced to the caesium frequency standard using an optical frequency comb^56,57 and a global navigation satellite system (GNSS)-referenced hydrogen maser (see Section 2.7 in the Supplementary Methods).

We switched between examining the 2S–6P_1/2 and 2S–6P_3/2 transitions several times during the measurement, except during measurement run C, for which only the 2S–6P_1/2 transition was examined for several values of α₀ (Extended Data Table 3).

Voigt and Voigt doublet line shapes

A Voigt line shape^23,58 is the convolution of a Lorentzian line shape (with FWHM linewidth Γ_L) and a Gaussian line shape (with FWHM linewidth Γ_G). It has a combined FWHM linewidth ${\varGamma }_{{\rm{F}}}\approx 0.5346{\varGamma }_{{\rm{L}}}\,+$ $\sqrt{0.2166{{\varGamma }_{{\rm{L}}}}^{2}+{{\varGamma }_{{\rm{G}}}}^{2}}$ (ref. ⁵⁹) and amplitude A and is centred on the resonance frequency ν₀. A constant offset y₀ is added to account for the experimentally observed signal background, resulting in five free parameters.

The Voigt doublet line shape is here defined as the sum of two Voigt line shapes with generally different resonance frequencies ν₁ and ν₂ and amplitudes A₁ and A₂ but equal Lorentzian and Gaussian linewidths²³ (and a constant offset y₀), resulting in seven free parameters. Its resonance frequency is the centre of mass of the constituent line shapes, that is, ν₀ = (A₁ν₁ + A₂ν₂)/(A₁ + A₂).

Data analysis

The resonance frequency ν₀ of each velocity group and detector of each line scan is determined by least-square fitting Voigt line shapes to the signal (for data with α₀ = 0 mrad, that is, data groups G1A–G12). For data with α₀ ≠ 0 mrad (data groups G13 and G14), in which the line can split into two Doppler components, the Voigt doublet line shape is used instead. For the fits, we assume the uncertainty on the signal y_j, that is, the number of fluorescence photons detected at detuning j, to be the photon-number shot (Poissonian) noise, given by $\sqrt{{y}_{j}}$ (because y_j ≫ 1, the Poisson distribution can be approximated with a normal distribution).

We use reduced chi-squared ${\chi }_{{\rm{red}}}^{2}={\chi }^{2}/k$ (with k degrees of freedom) as a measure of the goodness of fit. The average ${\chi }_{{\rm{red}}}^{2}$ is expected to be 1 if the fitted line shapes exactly match the experimental line shapes and if the signal fluctuations are fully described by shot noise. We first discuss the Voigt fits (k = 25), for which we find ${\chi }_{{\rm{red}}}^{2}$ to be substantially larger than 1 (up to ${\chi }_{{\rm{red}}}^{2}\approx 4.6$ at our highest spectroscopy laser power) for all but the slowest velocity groups. Only for those velocity groups, which have a comparatively lower signal and Doppler broadening, does ${\chi }_{{\rm{red}}}^{2}$ approach 1 (${\chi }_{{\rm{red}}}^{2}\approx 1.1$ for τ₁₆ for all data groups).

We identify two distinct contributions to the increased ${\chi }_{{\rm{red}}}^{2}$. First, there are small model deviations between the fitted and experimental line shapes, caused by non-Gaussian (and non-Lorentzian) broadening and saturation effects not included in the former and clearly observable in the fit residuals (up to approximately 2% deviation; see black circles at the top of Extended Data Fig. 1b). Our simulated line shapes (both LFS and QI simulations) include these effects and consequently show much better agreement with the experimental line shapes (see dashed and solid lines in Extended Data Fig. 1b). We use this to determine the effect of the deviations on ${\chi }_{{\rm{red}}}^{2}$ by repeating the line shape fits using simulated data instead of experimental data. In this Monte Carlo simulation, the appropriate line shape simulation is scaled and offset to match the experimental data of each line scan and then shot noise is added to the simulated signal. The simulated ${\chi }_{{\rm{red}}}^{2}$ values reproduce, and therefore the deviations explain, approximately 70% of the excess (that is, ${\chi }_{{\rm{red}}}^{2}-1$) in the experimental ${\chi }_{{\rm{red}}}^{2}$ values.

Second, there are fluctuations in the signal that lead to excess (technical) noise above shot noise, which we attribute to fluctuations in the atomic flux (of metastable 2S atoms). In particular, we identify correlations between ${\chi }_{{\rm{red}}}^{2}$ of a line scan and fluctuations of the nozzle temperature (Pearson correlation coefficient r = 0.45) and the preparation laser power (r = 0.26) during the line scan, both of which directly affect the number of 2S atoms reaching the spectroscopy region. The correlation with the spectroscopy laser power is much smaller (r = 0.03). We find that the simple assumption of a velocity-group-independent, 1% rms fluctuation of the signal from detuning to detuning explains, on average, the remaining excess of the experimental ${\chi }_{{\rm{red}}}^{2}$ values.

The ${\chi }_{{\rm{red}}}^{2}$ behaviour is very similar for the Voigt doublet fits (k = 23) to the α₀ = ±7.5 mrad data (data group G13). For the α₀ = ±12 mrad data (data group G14), the two Doppler components start to separate, particularly for fast velocity groups (Fig. 3c). This leads to large model deviations (up to 14%; see bottom of Extended Data Fig. 1b) from saturation effects, as some atoms interact with both spectroscopy laser beams (|Δ| ≲ Γ_2P), whereas others only interact with one beam (|Δ| ≳ Γ_2P). Consequently, ${\chi }_{{\rm{red}}}^{2}$ can exceed 20, which is largely explained (90% of excess) by the deviations, as again determined from the Monte Carlo simulation.

Asymmetric (about the line centre) deviations between the fitted and experimental line shapes, arising as a result of LFS and QI, do not substantially influence ${\chi }_{{\rm{red}}}^{2}$ because of their small size. However, both symmetric and asymmetric deviations lead to a sampling bias, as discussed in Section 2.5 in the Supplementary Methods.

The uncertainty of the experimental resonance frequency ν₀ is estimated from the line shape fits assuming only shot noise, that is, the technical noise is not taken into account at this point. The value of ν₀ for each velocity group and detector of each line scan is corrected for the LFS and QI shift by subtracting, respectively, ν_LFS and ν_QI, which are determined from the corresponding simulated line shapes (see Section 1.1 in the Supplementary Methods). The mean speed $\overline{v}$ and rms speed ${\overline{v}}_{{\rm{rms}}}$ of each velocity group are also determined from these simulated line shapes (see Section 1.1 in the Supplementary Methods; Extended Data Table 2 gives the average value of $\overline{v}$ for each velocity group). The second-order Doppler shift Δν_SOD is calculated using ${\overline{v}}_{{\rm{rms}}}$ (see Section 2.1 in the Supplementary Methods) and likewise subtracted from ν₀.

Next, using the simulated values of the speed $\bar{v}$, the Doppler shift extrapolation is performed to find the Doppler-free transition frequency ν_e and the Doppler slope κ. The values ν_e and κ found for each line scan are inherently strongly correlated (Pearson correlation coefficient r_e ≈ −0.97) and their uncertainties are found by propagating the uncertainties of ν₀. Although the averaging process outlined below reduces this correlation, the correlation remains substantial (r = −0.78) between the averaged values of ν_e and κ of different data groups. The LFS, QI shift and second-order Doppler shift all depend on the speed of the 2S atoms, either indirectly through the interaction time or directly. This results in non-zero Doppler slopes if not corrected for. In particular, the LFS, on average, would lead to κ ≈ −5 Hz (m s⁻¹)⁻¹ and it is only by accounting for it that the experimentally determined values of κ are, on average, compatible with zero.

The ${\chi }_{{\rm{red}}}^{2}$ of the Doppler shift extrapolation (k = 14) is close to 1 (${\chi }_{{\rm{red}}}^{2}=1.04(2)$ on average; standard deviation over data groups in parentheses), showing that the data are well described by a linear model and technical noise is small compared with shot noise. This contrasts with the excess noise observed in the line shape fits, as discussed above. We attribute this to the different timescales involved: the different velocity groups are recorded for about 100 μs and within 2,560 μs of each other, whereas the signal at each detuning is accumulated for 1 s before moving to the next detuning. That is, the Doppler shift extrapolation is mainly susceptible to technical noise on timescales of 100 μs, whereas the signal at different detunings is susceptible to technical noise on timescales of about 1 s, which is, for example, the timescale expected for nozzle temperature fluctuations.

Next we find the weighted mean of ν_e from the two detectors for each line scan (except when no data from the bottom detector are available, in which case data from the top detector are used), taking into account experimentally determined correlations (r = 0.36(15) on average). We attribute these correlations, which tend to increase with spectroscopy laser power and therefore the signal, again to the detuning-to-detuning fluctuations in the atomic flux that are common mode to both detectors (and the velocity groups). We then form the weighted mean of the detector-averaged ν_e for each freezing cycle in a given data group. The reduced chi-squared ${\chi }_{{\rm{red}},{\rm{FC}}}^{2}$ of this average is typically greater than 1 (${\bar{\chi }}_{{\rm{red}},{\rm{FC}}}^{2}=1.44(23)$ on average), which we attribute again to fluctuations in the atomic flux. We account for this excess scatter by scaling the uncertainty of ν_e by the corresponding $\sqrt{{\chi }_{{\rm{red}},{\rm{FC}}}^{2}}$ if ${\chi }_{{\rm{red}},{\rm{FC}}}^{2} > 1$. This procedure shifts the determined transition frequencies (by changing the weighting of the data) by less than 20 Hz, much smaller than the associated uncertainties. A weighted mean of the detector-averaged, uncertainty-scaled ν_e is formed for each data group and the remaining corrections are applied (Table 1 and Extended Data Table 4). Finally, the relevant data groups are (weighted) averaged to find the transition frequencies of the 2S–6P_1/2 and 2S–6P_3/2 transitions. Throughout the analysis, the weights of the averages are based only on the (scaled) statistical frequency uncertainty (including for the Doppler slope κ), with the (correlated) uncertainty of the corrections not included in the weights. The statistical weights w_2S–6P of the data groups for the determination of the 2S–6P fine-structure centroid ν_2S–6P are given in Extended Data Table 3.

The data analysis was blinded by adding a randomly chosen offset frequency to the transition frequencies. The offset frequency was only removed after all of the main systematic effects had been studied. Further small corrections, identified after the offset frequency was removed, resulted in a negligible shift of the determined transition frequencies of at most 10 Hz. The results of the data analysis (performed by L.M.) were confirmed by a second, independently implemented analysis (performed by V.W.).

Modelling of atomic beam and fluorescence line shape

The fluorescence line shape of the 2S–6P transition is modelled by a Monte Carlo simulation of the atomic beam as a set of atomic trajectories, the trajectories’ interaction with the 1S–2S preparation and 2S–6P spectroscopy lasers and their contribution to the fluorescence signal. The procedure is described in detail in Section 1.1 in the Supplementary Methods. Two complementary models describe the interaction with the spectroscopy laser, the QI model (see below and Section 1.2 in the Supplementary Methods) and the LFS model (see main text and Section 1.3 in the Supplementary Methods).

Speed distribution of atomic beam

We use the signal of the velocity groups as a time-of-flight measurement of the speed distribution of the atomic beam. To this end, we compare the experimental values of the line amplitudes A of the velocity groups to the values of A of line shapes simulated using a given speed distribution (see Section 1.1 in the Supplementary Methods). We find that the probability distribution of the speed v of atoms leaving the nozzle towards the 2S–6P spectroscopy region is well described by a modified Maxwell–Boltzmann flux distribution for a wide range of experimental parameters (see ref. ²³ for details). The flux distribution is given by

$${p}_{{\rm{eff}}}(v)={\mathcal{N}}{v}^{3}{e}^{-\frac{{m}_{{\rm{H}}}{v}^{2}}{2{k}_{{\rm{B}}}{T}_{{\rm{N}}}}}{e}^{-\frac{{v}_{{\rm{cut}}-{\rm{off}}}}{v}},$$

(12)

in which ${\mathcal{N}}$ is a normalization constant. The extra factor exp(−v_cut-off/v) accounts for the depletion of slower atoms through collisions inside the nozzle, inside the beam and with the background gas^60,61,62. A similar depletion has been observed in our 2S–4P measurement and other atomic hydrogen beams^3,63.

Using the above comparison of experimental data with simulations, v_cut-off is found to be 50 m s⁻¹ on average. Extended Data Table 3 lists the average value and variation for each data group. A substantial part of the variation is because of the fact that v_cut-off typically increases during a freezing cycle (see Fig. 6.1 of ref. ²³). This is because the accumulation of frozen hydrogen decreases the diameter of the nozzle, causing an increase in the gas pressure and therefore collisions inside the nozzle. We take this variation into account when determining (the uncertainty of) the mean speeds of the velocity groups and the simulation corrections (see Section 1.1 in the Supplementary Methods and Extended Data Table 5).

QI shift

We simulate QI-distorted line shapes with a model combining optical Bloch equations with simulations of the spatial detection efficiency, averaged over a set of trajectories representing the atomic beam (see Sections 1.1 and 1.2 in the Supplementary Methods). The QI shift is here defined as the centre frequency of a line shape fit to the simulated line shapes (see Section 1.1 in the Supplementary Methods). The validity of this approach was demonstrated by the excellent agreement between the observed and simulated QI shifts in our previous measurement of the 2S–4P transition², in which the shifts were more than sevenfold larger because of the smaller detection solid angle and larger linewidth²².

The simulated QI shifts, as a function of polarization angle θ_L, are found to be at most 7.1 kHz and −4.1 kHz for the 2S–6P_1/2 and 2S–6P_3/2 transitions at our highest spectroscopy laser power (used to give upper limits here and below), respectively. At the magic angle θ_L = 56.5°, the shifts reduce to at most −0.87(54) kHz and 0.45(27) kHz (including ±3° alignment uncertainty; again at the highest spectroscopy laser power). When we account for data taken at θ_L = 146.5° (see below) and at lower laser powers (with statistical weights as given in Extended Data Table 3), we obtain the overall simulated shifts (−0.25(36) kHz and 0.05(15) kHz) given in the main text. The cancellation inherent in the 2S–6P fine-structure centroid reduces the shift to at most −0.37 kHz at any polarization angle and to below 0.01 kHz at around θ_L = 56.5° (below the otherwise negligible ac-Stark shift; see Section 1.2 in the Supplementary Methods). Including all data results in the shift of −0.05(2) kHz given in the main text.

The magic angle θ_L = 56.5° used in the measurement was determined with simulations before the measurement began, whereas more refined simulations of the spatial detection efficiency (completed after the measurement and used for all simulation results given here) result in a magic angle of approximately 52°. Moreover, the magic angle also slightly shifts with laser power (by up to 2° for the powers used here; see Section 1.2 in the Supplementary Methods). However, the QI shifts are still strongly suppressed at the magic angle used, despite it being slightly different from the optimal value.

To test our QI model and simulations, a limited amount of data were taken at θ_L = 146.5° (Fig. 4 and Extended Data Table 3), that is, orthogonal to the magic polarization angle, which we compare with the data taken at θ_L = 56.5°. For the 2S–6P_1/2 transition, the difference in Doppler-free transition frequency of ν_e(θ_L = 146.5°) − ν_e(θ_L = 56.5°) = −0.01(1.69) kHz is in excellent agreement with 0 after correcting for a differential QI shift of 3.44(92) kHz and a differential Doppler shift of −1.42(1.42) kHz. We may also compare the experimental and simulated line shape distortions at θ_L = 146.5°, in which the QI shift dominates over the LFS, by comparing the asymmetry of the experimental and simulated fit residuals (Extended Data Fig. 1). We find excellent agreement, especially at detunings larger than the linewidth, for which the line shape distortions from QI are largest.

For the 2S–6P_3/2 transition, we find a moderate (2.3 standard deviations) tension with a difference of ν_e(θ_L = 146.5°) − ν_e(θ_L = 56.5°) = 4.08(1.77) kHz in the transition frequency, having corrected for a differential QI shift of −1.78(47) kHz. The removed differential Doppler shift is likewise significantly non-zero (−3.66(1.68) kHz). This correlation is consistent with, but not conclusive evidence for, the non-zero difference being caused by random errors affecting the Doppler shift extrapolation. This conclusion is also supported by the fact that there is no tension in the velocity-group-averaged resonance frequency, that is, assuming zero Doppler shift (see Fig. 6.9 of ref. ²³). Furthermore, we find the line shape distortions at θ_L = 146.5° to be compatible with our QI simulations but incompatible with a QI shift of opposite sign and twice the magnitude as implied by the measured difference (Extended Data Fig. 1). We therefore conclude that the tension probably results from random errors in the determination of the resonance frequencies.

2S–6P fine-structure centroid, 6P fine-structure splitting and HFS corrections

The 2S–6P fine-structure centroid ν_2S–6P is the transition frequency from the 2S HFS centroid to the 6P fine-structure centroid. It is determined from the two measured transition frequencies ν_1/2 and ν_3/2 for the transitions from the ${2{\rm{S}}}_{1/2}^{F=0}$ level to the ${6{\rm{P}}}_{1/2}^{F=1}$ level (2S–6P_1/2 transition) and the ${6{\rm{P}}}_{3/2}^{F=1}$ level (2S–6P_3/2 transition), respectively, by first correcting ν_1/2 and ν_3/2 for the 2S and 6P HFS and then averaging the corrected ν_1/2 and ν_3/2 weighted by their fine-structure multiplicity ratio of 1:2 (equivalent to the ratio of the line strengths ∝μ² of the 2S–6P_1/2 and 2S–6P_3/2 transitions, in which μ is the dipole moment) to find the 6P fine-structure centroid. This results in equation (7), with the HFS corrections included in Δν_HFS(ν_2S–6P), as detailed below.

The hyperfine interaction splits the fine-structure levels 2S_1/2, 6P_1/2 and 6P_3/2 into doublets^64,65. The relevant HFS levels ${2{\rm{S}}}_{1/2}^{F=0}$, ${6{\rm{P}}}_{1/2}^{F=1}$ and ${6{\rm{P}}}_{3/2}^{F=1}$ are shifted from the fine-structure levels by the HFS energies $\Delta {\nu }_{{\rm{HFS}}}({2{\rm{S}}}_{1/2}^{F=0})$, $\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{1/2}^{F=1})$ and $\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{3/2}^{F=1})$, respectively (see Fig. 6.11 of ref. ²³ for the relevant level scheme). The value of $\Delta {\nu }_{{\rm{HFS}}}({2{\rm{S}}}_{1/2}^{F=0})$ and its uncertainty are obtained from a measurement⁶⁶ of the 2S HFS splitting Δν_HFS(2S_1/2) as

$$\Delta {\nu }_{{\rm{HFS}}}({2{\rm{S}}}_{1/2}^{F=0})=-(3/4)\Delta {\nu }_{{\rm{HFS}}}({2{\rm{S}}}_{1/2})=-\mathrm{133,167,625.7}(5.0)\,{\rm{Hz}}.$$

(13)

$\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{1/2}^{F=1})$ and $\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{3/2}^{F=1})$ can be calculated as detailed in refs. ^64,65. They include small corrections from off-diagonal elements in the HFS Hamiltonian, which mix HFS levels with the same value of F but different values of J. Because only the F = 1 level of each HFS doublet is shifted by this effect, the centres of gravity of the HFS doublets are shifted by $\Delta {\nu }_{{\rm{HFS}}}^{{\rm{o}}.{\rm{d}}.}({6{\rm{P}}}_{1/2})$ and $\Delta {\nu }_{{\rm{HFS}}}^{{\rm{o}}.{\rm{d}}.}({6{\rm{P}}}_{3/2})$. Using the values for the 6P HFS splittings Δν_HFS(6P_1/2), Δν_HFS(6P_3/2) and the values for $\Delta {\nu }_{{\rm{HFS}}}^{{\rm{o}}.{\rm{d}}.}({6{\rm{P}}}_{1/2})$, $\Delta {\nu }_{{\rm{HFS}}}^{{\rm{o}}.{\rm{d}}.}({6{\rm{P}}}_{3/2})$ given in Table 1 of ref. ⁶⁴ (see also equations (29) and (30) in ref. ⁶⁵ and comments therein), we find

$$\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{1/2}^{F=1})=(1/4)\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{1/2})+\Delta {\nu }_{{\rm{HFS}}}^{{\rm{o}}.{\rm{d}}.}({6{\rm{P}}}_{1/2})=\mathrm{547,798}(6)\,{\rm{Hz}},$$

(14)

$$\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{3/2}^{F=1})=-(5/8)\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{3/2})+\Delta {\nu }_{{\rm{HFS}}}^{{\rm{o}}.{\rm{d}}.}({6{\rm{P}}}_{3/2})=-\mathrm{547,460}(6)\,{\rm{Hz}}.$$

(15)

$\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{1/2}^{F=1})$ and $\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{3/2}^{F=1})$ are assumed to be fully correlated.

The resulting HFS correction of the 2S–6P fine-structure centroid ν_2S–6P is

$$\begin{array}{l}\Delta {\nu }_{{\rm{HFS}}}({\nu }_{2{\rm{S}}-6{\rm{P}}})\,=\,-(1/3)\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{1/2}^{F=1})\\ \,-(2/3)\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{3/2}^{F=1})+\Delta {\nu }_{{\rm{HFS}}}({2{\rm{S}}}_{1/2}^{F=0})\\ \,=\,-\mathrm{132,985,250}(10)\,{\rm{Hz}},\end{array}$$

(16)

in which we rounded to the nearest 10 Hz, as done for all corrections.

SM predictions of transition frequencies and bound-state QED test

We find the SM prediction ν_2S–6P,SM of the 2S–6P fine-structure centroid using

$${\nu }_{2{\rm{S}}-6{\rm{P}},{\rm{SM}}}=\frac{(1/3){E}_{6,1,1/2}+(2/3){E}_{6,1,3/2}-{E}_{2,0,1/2}}{{E}_{2,0,1/2}-{E}_{1,0,1/2}}{\nu }_{1{\rm{S}}-2{\rm{S}}}=\frac{E(2{\rm{S}}-6{\rm{P}})}{E(1{\rm{S}}-2{\rm{S}})}{\nu }_{1{\rm{S}}-2{\rm{S}}},$$

(17)

in which E_nlJ are the fine-structure level energies from equation (1) and ν_1S–2S is the measured frequency of the 1S–2S hyperfine centroid¹⁸. This parametrization removes the explicit dependence of E_nlJ on R_∞. Using the muonic value of r_p (ref. ¹⁵), we find the value of ν_2S–6P,SM given in equation (10).

Extended Data Table 1 lists the contributions to ν_2S–6P,SM. Along with the Dirac eigenvalue ($c{R}_{\infty }{f}_{{nJ}}^{\mathrm{Dirac}}$ of equation (1); equation (30) in ref. ¹), we list the individual QED corrections ($c{R}_{{\infty }}{f}_{{nlJ}}^{\mathrm{QED}}$ and $c{R}_{\infty }{\delta }_{l0}({C}_{\mathrm{NS}}/{n}^{3})\,{r}_{{\rm{p}}}^{2}$ of equation (1); equations (32)–(64) in ref. ¹), with the sum of the corrections corresponding to the Lamb shift ${\mathcal{L}}$ (${\mathcal{L}}(nlJ)$ for a single fine-structure level; ${\mathcal{L}}(2{\rm{S}}-6{\rm{P}})=(1/3){\mathcal{L}}(6,1,1/2)+(2/3){\mathcal{L}}(6,1,3/2)-{\mathcal{L}}(2,0,1/2)$ for the 2S–6P fine-structure centroid). Extended Data Table 1 also gives the QED-only uncertainty, which we define as the uncertainty excluding contributions from r_p, α, m_p/m_e and ν_1S–2S. All listed QED corrections scale as cR_∞C/n³ in leading order for S-states, in which cR_∞C is the corresponding leading-order QED correction to the 1S level. This includes the (leading order, ∝α² × α², with the first α² factor absorbed in R_∞ = α²m_ec/2h in equation (1)) nuclear size correction highlighted in equation (1), for which $C={C}_{{\rm{NS}}}{r}_{{\rm{p}}}^{2}$. Therefore, the corrections between different S-states are correlated, which is taken into account in the uncertainty of ν_2S–6P,SM. Non-S-states have generally much smaller corrections (for example, the fractional corrections are 1.3 × 10⁻⁶ of the 2S binding energy but 4.4 × 10⁻⁹ of the 6P binding energy) and, in particular, their nuclear size corrections are at present negligible (at most 7 × 10⁻¹⁶ of the 6P binding energy). There is no correlation between the different QED corrections and we find the total QED-only uncertainty of 179 Hz by adding the uncertainties of the corrections in quadrature. Overall, E(2S–6P) and E(1S–2S) are highly correlated (r = 0.995 if only considering QED-only uncertainty).

The other dominant source of uncertainty for ν_2S–6P,SM is the muonic value of r_p, which contributes 138 Hz to the uncertainty of ν_2S–6P,SM. Although the uncertainty of r_p itself partly originates from QED corrections¹⁵, the QED predictions for the energy levels of hydrogen and muonic hydrogen are uncorrelated at the present level of accuracy¹ and we therefore treat the QED-only uncertainty and the uncertainty from r_p as uncorrelated. The uncertainty contributions from α (1.7 Hz), m_p/m_e (0.1 mHz) and ν_1S–2S (3 Hz) are negligible. In total, this results in an uncertainty of 226 Hz on ν_2S–6P,SM.

It is instructive to find the sensitivity of a prediction ν_SM, derived in the same way as ν_2S–6P,SM, to changes in C. Making use of the 1/n³ scaling of the QED corrections (and using the approximation E_nlJ ≈ chR_∞(−1/n² + δ_l0C/n³), that is, ignoring all non-leading-order corrections to ${f}_{{nJ}}^{{\rm{Dirac}}}$ and all QED corrections except C), we find

$$\frac{{\rm{\partial }}}{{\rm{\partial }}C}\left(\frac{{\nu }_{{\rm{S}}{\rm{M}}}(n,{n}^{{\prime} },\mathop{n}\limits^{ \sim },{\mathop{n}\limits^{ \sim }}^{{\prime} })}{c{R}_{\infty }}\right)\approx \left(\frac{{\delta }_{l0}}{{n}^{3}}-\frac{{\delta }_{{l}^{{\prime} }0}}{{n}^{{\prime} 3}}\right)-\left(\frac{{\delta }_{\mathop{l}\limits^{ \sim }0}}{{\mathop{n}\limits^{ \sim }}^{3}}-\frac{{\delta }_{{\mathop{l}\limits^{ \sim }}^{{\prime} }0}}{{\mathop{n}\limits^{ \sim }}^{{\prime} 3}}\right)\frac{1/{n}^{2}-1/{n}^{{\prime} 2}}{1/{\mathop{n}\limits^{ \sim }}^{2}-1/{\mathop{n}\limits^{ \sim }}^{{\prime} 2}},$$

(18)

in which n′, l′ → n, l is the transition to be predicted (for example, 2S–6P transition for ν_2S–6P,SM) and ${\tilde{n}}^{{\prime} },\,{\tilde{l}}^{{\prime} }\to \tilde{n},\,\tilde{l}$ is the measured transition used as input (for example, 1S–2S transition for ν_2S–6P,SM). The sensitivity of ν_2S–6P,SM is ∂(ν_2S–6P,SM/cR_∞)/∂C = 0.134. By contrast, using the 1S–3S transition instead of the 2S–6P transition leads to a 1.8-fold lower sensitivity (∂(ν_SM/cR_∞)/∂C = 0.074) because the relative contribution of C to the 1S–3S transition frequency is approximately twice as large as for the 2S–6P transition frequency. Combined with its 1.5-fold smaller uncertainty, ν_2S–6P therefore tests C with 2.7-fold higher precision than the 1S–3S measurement⁵. Because the nuclear size correction $c{R}_{\infty }{C}_{\mathrm{NS}}\,{r}_{{\rm{p}}}^{2}/{n}^{3}$ scales as 1/n³ like the other bound-state QED corrections cR_∞C/n³, comparing r_p found from atomic hydrogen and from muonic hydrogen is a test of bound-state QED, as any missing or miscalculated terms in atomic hydrogen of the form cR_∞C/n³ would lead to a discrepancy. Furthermore, the precision with which r_p can be extracted from a given combination of measurements is therefore a direct measure of the precision of the implied QED test. Note that, because Extended Data Table 1 lists the corrections of ν_2S–6P,SM, which are approximately −cR_∞C/2³, the sensitivity relative to the listed corrections is −8 × 0.134 = −1.072. For example, artificially removing the hadronic vacuum polarization shifts ν_2S–6P,SM by −1.072 × 425.1 Hz = −0.46 kHz, or approximately one experimental σ of ν_2S–6P.

We may also extract the 1S Lamb shift ${\mathcal{L}}(1{\rm{S}})$ by writing equation (1) as

$${E}_{{nlJ}}=ch{R}_{\infty }{f}_{{nJ}}^{\mathrm{Dirac}}+{\delta }_{0l}\frac{h{\mathcal{L}}(1{\rm{S}})}{{n}^{3}}+h\delta {\mathcal{L}}(nlJ),$$

(19)

in which ${\mathcal{L}}(1{\rm{S}})\equiv {\mathcal{L}}(1,0,1/2)=c{R}_{\infty }({f}_{1,0,1/2}^{\mathrm{QED}}+{C}_{\mathrm{NS}}{r}_{{\rm{p}}}^{2})$ and $\delta {\mathcal{L}}(nlJ)={\mathcal{L}}(nlJ)\,-$ ${\delta }_{0l}{\mathcal{L}}(1{\rm{S}})/{n}^{3}$ is the state-specific Lamb shift. By combining equation (19) for the 2S–6P and 1S–2S transitions and using ν_2S–6P and ν_1S–2S as inputs, we find ${{\mathcal{L}}}_{\exp }(1{\rm{S}})={\mathrm{8,172,744.13}(14)}_{{\rm{QED}}}{(3.56)}_{\exp }\,{\rm{kHz}}\,=$ $\mathrm{8,172,744.1}(3.6)\,{\rm{kHz}}$. Terms proportional to state-specific Lamb shifts contribute 224 MHz to ${{\mathcal{L}}}_{\exp }(1{\rm{S}})$. The uncertainty is dominated by the uncertainty of ν_2S–6P (‘exp’), with the QED uncertainty of the state-specific Lamb shifts (‘QED’) being much smaller and contributions from ν_1S–2S (22 Hz) and physical constants (10 Hz from α; m_p/m_e, r_p, R_∞ less than 0.1 Hz) negligible. As expected from the discussion above, ${{\mathcal{L}}}_{\exp }(1{\rm{S}})$ is 2.7-fold more precise than the next best determination using the 1S–3S measurement⁵.

The corresponding QED prediction of the 1S Lamb shift is found by combining equation (1) with the muonic value of r_p, giving ${{\mathcal{L}}}_{{\rm{QED}}}(1{\rm{S}})\,=$${\mathrm{8,172,744.1}(1.3)}_{{\rm{QED}}}{(1.0)}_{{{\rm{r}}}_{{\rm{p}}}}\,{\rm{kHz}}=\mathrm{8,172,744.1}(1.7)\,{\rm{kHz}}$. Its uncertainty is dominated by both QED uncertainty and the uncertainty of r_p, whereas other sources are negligible (3 Hz from α; m_p/m_e, R_∞ less than 0.01 Hz). ${{\mathcal{L}}}_{\exp }(1{\rm{S}})$ and ${{\mathcal{L}}}_{{\rm{QED}}}(1{\rm{S}})$ are uncorrelated, as their respective QED uncertainties are uncorrelated¹. They are in excellent agreement and test the 1S Lamb shift and thereby bound-state QED corrections to 0.5 ppm. Complementary tests of bound-state QED in strong electromagnetic fields with highly charged ions at present achieve a relative precision of 1 × 10⁻⁴ but can be more sensitive to terms of high order in (Zα) (Z is the nuclear charge number; omitted elsewhere here because Z = 1 for atomic hydrogen)^47,67,68.

Finally, the QED prediction Δν_FS,QED(6P) for the 6P fine-structure splitting between the ${6{\rm{P}}}_{1/2}^{F=1}$ and ${6{\rm{P}}}_{3/2}^{F=1}$ levels is (using equations (14) and (15))

$$\begin{array}{l}\Delta {\nu }_{{\rm{FS}},{\rm{QED}}}(6{\rm{P}})\,=\,{E}_{6,1,3/2}/h-{E}_{6,1,1/2}/h+\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{3/2}^{F=1})\\ \,-\Delta {\nu }_{{\rm{HFS}}}({6{\rm{P}}}_{1/2}^{F=1})\\ \,=\,\mathrm{405,164.51}(1)\,{\rm{kHz}}.\end{array}$$

(20)

The nuclear size corrections in Δν_FS,QED(6P) are of order α² × α⁴ and α² × α⁵ and amount to 70 mHz, as the leading-order correction term $c{R}_{{\infty }}{C}_{\mathrm{NS}}{r}_{{\rm{p}}}^{2}\propto {\alpha }^{2}\times {\alpha }^{2}$ of equation (1) and corrections of order α² × α³ only apply to S-states¹.

dc-Stark shift

Static stray electric fields in the 2S–6P spectroscopy region can lead to a dc-Stark shift of the observed transition frequency. Here the dc-Stark shift Δν_dc is well described as quadratic in strength E = |E| of the electric field E in all relevant experimental regimes, that is,

$$\Delta {\nu }_{{\rm{dc}}}={\beta }_{{\rm{dc}}}{E}^{2},$$

(21)

in which β_dc is the applicable quadratic dc-Stark shift coefficient. We distinguish two experimentally relevant field strength regimes: the stray-field regime (E < 1 V m⁻¹), which covers the range of stray electric fields present in the experiment, and the bias-field regime (E = 10–45 V m⁻¹), which covers the range of applied bias fields used to determine the stray electric fields. Notably, although equation (21) is found to approximately hold in either regime, the coefficient β_dc may differ, as is the case for the 2S–6P_3/2 transition (Section 1.4 in the Supplementary Methods). The quadratic behaviour arises because the energy levels contributing to the net shift are well separated in energy from the perturbed level in either of our regimes. However, the shift of the involved levels between the regimes can lead to substantially different energy separations and thereby different values of β_dc.

The Faraday cage surrounding the spectroscopy region (Fig. 2b) shields it from external electric fields, including those used to draw the photoelectrons to the channel electron multipliers (whose input surfaces are held at 270 V; see Section 4.6.2 of ref. ²³). The colloidal graphite coating on all surfaces of the Faraday cage suppresses stray electric fields from the surfaces themselves (from charged oxide layers, contact potentials from dissimilar conductors or local changes in the work function) by, ideally, forming a uniform conductive layer with a uniform work function (see Section 4.6.1 of ref. ²³). However, effects such as imperfect shielding of external fields, imperfect graphite coating or temperature gradients leading to thermoelectric voltages or gradients in the work function can prevent the complete suppression of stray fields.

To address this, we measure the stray electric field by applying voltages to the six electrodes forming the Faraday cage (meshes at the top and bottom and four equal-sized segments of the cylinder wall) and using the atoms themselves as field sensors (see Section 4.6.7 of ref. ²³), similar to approaches in refs. ^5,69. Equal and opposite bias voltages are applied to opposing electrodes to create a bias electric field ${\bf{E}}={E}_{i}\hat{{\bf{i}}}$ with strength |E_i| = 10–45 V m⁻¹ along the given direction (i = x, y, z, as defined in Fig. 2b). By measuring the shifted 2S–6P transition frequency ν_e(E_i) from a fit to the fluorescence line shape of several line scans with opposite-polarity values of E_i and using the quadratic dependence ν_e(E_i) = β_dc,i(E_i − ΔE_i)² + ν_e(E_i = 0 V m⁻¹), we determine the stray electric field component ΔE_i along the given direction. This measurement also yields experimental values of β_dc,i at the bias field strengths for each transition. Extended Data Fig. 3 shows examples of such stray field measurements for both the 2S–6P_1/2 and 2S–6P_3/2 transitions, along with simulation results (see Section 1.4 in the Supplementary Methods). On average, each measurement includes eight line scans with non-zero bias field and there are 98 and 21 measurements for the 2S–6P_1/2 and 2S–6P_3/2 transitions, respectively. The stray electric field components determined during the three measurement runs are shown in Extended Data Fig. 4, in which we only include measurements using the 2S–6P_1/2 transition because using the 2S–6P_3/2 transition gives compatible, but substantially larger uncertainty, values of ΔE_i. Overall, the stray electric field has a strength less than 1 V m⁻¹ and predominantly points along the axis of the detector cylinder (the y-direction).

Using these stray field measurements, we estimate the dc-Stark shift correction and its uncertainty for the transition frequencies. The determination of the relevant quadratic dc-Stark shift coefficients in the stray-field regime by the use of experimentally verified simulations is described in Section 1.4 in the Supplementary Methods. The weighted mean and standard deviation of each stray electric field component ΔE_i are determined over each of the three measurement runs, using the 2S–6P_1/2 stray field measurements, as shown in Extended Data Fig. 4. We treat each measurement run separately to account for differences in the detector assembly (the meshes in the detector cylinder were replaced between run A and run B; see Section 4.6.1 of ref. ²³) and the month-long breaks in between the runs. Furthermore, we opt to use the standard deviation of the stray field components to estimate the dc-Stark shift uncertainty because we believe at least part of the variation of the stray fields to be physical in origin (as opposed to unaccounted excess measurement scatter) but are not confident that the resulting variations in the dc-Stark shift will average out. With this, we find dc-Stark shifts Δν_dc of 0.20(21) kHz and −0.02(6) kHz for the 2S–6P_1/2 and 2S–6P_3/2 transitions, respectively, in which the uncertainty is dominated by the stray electric fields in the first case and by coefficients in the second case, and shifts for both transitions mainly determined by the dominant stray electric field component along the y-direction. ν_1/2 and ν_3/2 have been corrected for the dc-Stark shift by subtracting the corresponding value. The Pearson correlation coefficient of the correction between the 2S–6P_1/2 and 2S–6P_3/2 transitions is found to be r = −0.30 by propagation of uncertainty.