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Fundamental Constants

Atomic, molecular, and optical experiments do not merely use fundamental constants. They help determine them. Recoil interferometers connect photon momentum to atomic mass, trapped particles compare spin and orbital frequencies in the same magnetic field, and precision spectra compare measured transition frequencies with bound-state quantum electrodynamics (QED). A global adjustment then combines these heterogeneous observations into a self-consistent set of constants and covariances.

This process is an inverse problem, not a cataloguing exercise. A quoted value such as

α−1=137.035 999 177(21)\alpha^{-1}=137.035\,999\,177(21)

is the output of the 2022 Committee on Data (CODATA) adjustment. It is not a single direct reading, and the parentheses are not a guarantee that every high-precision input agreed before statistical treatment. In the fine-structure-constant sector, several exceptionally precise inputs remain in tension.

The practical questions are therefore:

  • Which quantities are exact by definition, which are adjusted from data, and which are derived?
  • What observational equation connects each apparatus to the constants?
  • Which theory terms and auxiliary constants enter that equation?
  • Which uncertainties are shared, and which correlations survive into the recommended values?
  • Does a newer publication update an input datum, or has an international adjustment actually superseded the recommendation?

The answers matter whenever constants are used to test QED, convert between units, interpret spectroscopy, or search for physics beyond the Standard Model.

Constants is the quick-lookup home for recommended numerical values and defining SI constants. Atomic Units and Scales owns the derivation and use of the Bohr radius, Hartree energy, Rydberg energy, and related atomic scales. Precision Spectroscopy owns line-centre estimation, correction budgets, frequency ratios, and the experimental route from resonance to a calibrated frequency.

This page instead owns the constant-inference layer:

  • the distinction among defining, adjusted, and derived constants;
  • observational equations for α\alpha, R∞R_\infty, mass ratios, and magnetic-moment ratios;
  • the logic of a correlated CODATA least-squares adjustment;
  • the present experimental consistency of the leading AMO inputs;
  • the role of atomic and molecular structure theory in extracting constants; and
  • the reporting information needed to reproduce or reuse a determination.

Variation of Constants Searches owns temporal, spatial, oscillatory, and transient signals. Here it is enough to establish the essential rule: only a variation of a dimensionless combination can be stated without choosing a unit convention.

In the present International System of Units (SI), it is useful to separate three statuses.

StatusMeaningAMO examples
DefiningA stipulated exact numerical value realizes the unit system.cc, hh, ee, the caesium-133 hyperfine frequency ΔνCs\Delta\nu_{\mathrm{Cs}}
AdjustedA value and covariance are inferred from an evaluated body of experimental and theoretical input data.α\alpha, R∞R_\infty, Ar(e)A_{\mathrm r}(e), mp/mem_p/m_e, magnetic-moment ratios
DerivedA value follows algebraically from defining and adjusted quantities.μ0\mu_0, ϵ0\epsilon_0, a0a_0, EhE_h, μB\mu_B in SI units

The categories depend partly on the unit definition. Since 20 May 2019, hh, ee, and cc have exact SI values, whereas the vacuum magnetic permeability is no longer exactly 4π×10−7 N A−24\pi\times10^{-7}\ {\rm N\,A^{-2}}. Instead,

μ0=2αhe2c,ϵ0=1μ0c2.\mu_0 = \frac{2\alpha h}{e^2c}, \qquad \epsilon_0 = \frac{1}{\mu_0c^2}.

Thus an improved value of α\alpha improves the SI values of both μ0\mu_0 and ϵ0\epsilon_0. The physical content has not changed; the allocation between exact definitions and experimentally inferred numbers has.

The fine-structure constant

α=e24πϵ0ℏc\alpha = \frac{e^2}{4\pi\epsilon_0\hbar c}

and the mass ratio mp/mem_p/m_e are dimensionless. Their numerical values do not depend on whether one uses SI, Gaussian, atomic, or natural units. Their determination can therefore be compared across unit conventions without conversion.

By contrast, the numerical values of R∞R_\infty in m−1\mathrm{m^{-1}}, mem_e in kilograms, or μB\mu_B in J T−1\mathrm{J\,T^{-1}} depend on the unit definitions. These quantities are still physically meaningful and measurable, but statements about a hypothetical change must identify the reference standard. This is why a claim that a dimensional constant alone “varies” is incomplete.

Let y\mathbf y collect measured inputs and x\mathbf x the constants to be adjusted. Each datum has an observational equation

yi≐fi(x,η),y_i \doteq f_i(\mathbf x,\boldsymbol\eta),

where η\boldsymbol\eta denotes auxiliary quantities and calculated corrections. The symbol ≐\doteq emphasizes that this is the equation used for inference, not necessarily a defining identity. Examples include

hmRb≐α2c2R∞Ar(e)Ar(Rb),aeexp≐aeSM(α),νH,iexp≐νH,ith(R∞,rp,α,mpme,…),νLνc≐gionth2qeqionmionme.\begin{aligned} \frac{h}{m_{\mathrm{Rb}}} &\doteq \frac{\alpha^2c}{2R_\infty} \frac{A_{\mathrm r}(e)}{A_{\mathrm r}(\mathrm{Rb})}, \\ a_e^{\mathrm{exp}} &\doteq a_e^{\mathrm{SM}}(\alpha), \\ \nu_{\mathrm H,i}^{\mathrm{exp}} &\doteq \nu_{\mathrm H,i}^{\mathrm{th}} \left( R_\infty,r_p,\alpha,\frac{m_p}{m_e},\ldots \right), \\ \frac{\nu_{L}}{\nu_c} &\doteq \frac{g_{\mathrm{ion}}^{\mathrm{th}}}{2} \frac{q_e}{q_{\mathrm{ion}}} \frac{m_{\mathrm{ion}}}{m_e}. \end{aligned}

An experimental paper may report h/mRbh/m_{\mathrm{Rb}}, a transition frequency, or a frequency ratio. Calling its converted value “a measurement of α\alpha” is convenient, but the conversion also uses R∞R_\infty, relative masses, electromagnetic theory, and their covariances.

Network from AMO observables through a correlated adjustment to fundamental constants and derived quantities.

AMO constant determinations form an observational network. Arrows represent both exact identities and theory-dependent observational equations; a global adjustment must retain their covariance and theoretical corrections.

Suppose the measured input vector has covariance matrix VyV_y. Near a reference point x0\mathbf x_0, linearize the observational equations:

f(x)≃f(x0)+A δx,Aij=∂fi∂xj∣x0.\mathbf f(\mathbf x) \simeq \mathbf f(\mathbf x_0) + A\,\delta\mathbf x, \qquad A_{ij} = \left. \frac{\partial f_i}{\partial x_j} \right|_{\mathbf x_0}.

With

d=y−f(x0),\mathbf d = \mathbf y-\mathbf f(\mathbf x_0),

the generalized least-squares estimate minimizes

χ2=(d−Aδx)TVy−1(d−Aδx).\chi^2 = \left( \mathbf d-A\delta\mathbf x \right)^{\mathsf T} V_y^{-1} \left( \mathbf d-A\delta\mathbf x \right).

When the normal matrix is nonsingular,

δx^=(ATVy−1A)−1ATVy−1d,\widehat{\delta\mathbf x} = \left( A^{\mathsf T}V_y^{-1}A \right)^{-1} A^{\mathsf T}V_y^{-1}\mathbf d,

and, in the linear-Gaussian approximation,

Vx=(ATVy−1A)−1.V_x = \left( A^{\mathsf T}V_y^{-1}A \right)^{-1}.

The off-diagonal elements of VxV_x are part of the result. A later calculation involving two adjusted constants must use

u2(g)=∇gTVx∇g,u^2(g) = \boldsymbol\nabla g^{\mathsf T} V_x \boldsymbol\nabla g,

not add the two quoted marginal uncertainties in quadrature while silently setting their correlation to zero.

Correlations enter at several levels:

  1. Two frequencies may share the same clock, comb, magnetic-field calibration, or line-shape model.
  2. Several theoretical predictions may share an uncalculated QED coefficient or a nuclear radius.
  3. One input value may already be a least-squares result with internal covariance.
  4. The adjustment itself couples constants because one observable depends on several of them.

For example, hydrogen spectroscopy determines a narrow combination of R∞R_\infty and rpr_p, so the adjusted values can be strongly correlated even if the raw transition measurements were independent. Ignoring that correlation can make a derived transition prediction look either artificially precise or artificially uncertain.

Residuals, inconsistency, and uncertainty expansion

Section titled “Residuals, inconsistency, and uncertainty expansion”

For input ii, a normalized residual is schematically

ri=yi−fi(x^)uieff,r_i = \frac{ y_i-f_i(\widehat{\mathbf x}) }{ u_i^{\mathrm{eff}} },

where uieffu_i^{\mathrm{eff}} must include the relevant covariance with the adjusted prediction. Large residuals signal that the adopted uncertainty model does not describe the input set well.

CODATA may apply a common expansion factor to selected uncertainties before the final adjustment. This is an explicit, documented response to inconsistent data. It does not identify which experiment is biased, erase the disagreement, or convert incompatible results into independent confirmation.

In the 2022 adjustment:

  • uncertainties of six leading fine-structure-constant inputs were multiplied by 2.52.5;
  • the unexpanded normalized residual of the 2018 caesium recoil result was about 4.74.7; and
  • uncertainties of selected hydrogen and deuterium transition data were multiplied by 1.71.7 because their scatter exceeded the adopted model.

These facts belong beside the recommended numbers whenever the result is used as evidence for consistency.

As of 25 July 2026, the NIST Fundamental Constants Data Center lists CODATA 2022 as the current internationally recommended set. Its input cutoff was 31 December 2022. The next regular adjustment is CODATA 2026, whose data cutoff is 31 December 2026; it is therefore not yet available.

Newer measurements can be more precise than the current recommendation and can foreshadow a future adjustment. They should be labelled post-CODATA 2022, not silently substituted into a table headed “recommended constants.”

The following rounded values are useful for discussing the inference network. Use the Constants table or the official NIST database for machine-facing work.

QuantityCODATA 2022 valueRelative standard uncertainty
α−1\alpha^{-1}137.035 999 177(21)137.035\,999\,177(21)1.5×10−101.5\times10^{-10}
R∞R_\infty10 973 731.568 157(12) m−110\,973\,731.568\,157(12)\ {\rm m^{-1}}1.1×10−121.1\times10^{-12}
mp/mem_p/m_e1836.152 673 426(32)1836.152\,673\,426(32)1.7×10−111.7\times10^{-11}
μe/μB\mu_e/\mu_B−1.001 159 652 180 46(18)-1.001\,159\,652\,180\,46(18)1.8×10−131.8\times10^{-13}
μp/μN\mu_p/\mu_N2.792 847 344 63(82)2.792\,847\,344\,63(82)2.9×10−102.9\times10^{-10}
μn/μN\mu_n/\mu_N−1.913 042 76(45)-1.913\,042\,76(45)2.4×10−72.4\times10^{-7}

The digits in parentheses are one-standard-deviation uncertainties in the last quoted digits. They are marginal uncertainties; they do not display the correlations among entries.

The fine-structure constant sets the dimensionless strength of the electromagnetic interaction:

α=e24πϵ0ℏc≃1137.\alpha = \frac{e^2}{4\pi\epsilon_0\hbar c} \simeq \frac{1}{137}.

In nonrelativistic atomic physics, it relates characteristic scales:

vBohrc∼α,EfineEgross∼α2.\frac{v_{\mathrm{Bohr}}}{c} \sim \alpha, \qquad \frac{E_{\mathrm{fine}}}{E_{\mathrm{gross}}} \sim \alpha^2.

In QED it is the perturbative expansion parameter, although coefficients, logarithms, bound-state factors such as ZαZ\alpha, and nonperturbative effects determine the accuracy of any particular truncation.

Because ee, hh, and cc are exact in the current SI,

μ0=2αhe2c\mu_0 = \frac{2\alpha h}{e^2c}

is now an experimentally inferred quantity. Statements that μ0\mu_0 is exact refer to the pre-2019 SI.

Combining

R∞=α2mec2hR_\infty = \frac{\alpha^2m_ec}{2h}

with the relative atomic masses

Ar(X)=mXmu,Ar(e)=memu,A_{\mathrm r}(X) = \frac{m_X}{m_u}, \qquad A_{\mathrm r}(e) = \frac{m_e}{m_u},

gives the recoil observational equation

α2=2R∞cAr(X)Ar(e)hmX.\alpha^2 = \frac{2R_\infty}{c} \frac{A_{\mathrm r}(X)}{A_{\mathrm r}(e)} \frac{h}{m_X}.

An atom interferometer measures the response to known photon momentum. For a two-level momentum separation ℏk\hbar k, the single-photon recoil angular frequency is

ωr=ℏk22mX.\omega_r = \frac{\hbar k^2}{2m_X}.

Large-momentum-transfer pulses or Bloch oscillations amplify the phase associated with h/mXh/m_X. The final value of α\alpha also requires Ar(X)/Ar(e)A_{\mathrm r}(X)/A_{\mathrm r}(e) and R∞R_\infty. The method is largely independent of the electron-anomaly route, which makes the comparison especially valuable.

The leading experimental issues include:

  • wavefront curvature and Gouy phase, which change the effective photon momentum;
  • spatial sampling of the optical field by a finite-temperature cloud;
  • gravity gradients, Coriolis acceleration, and trajectory mismatch;
  • light shifts, diffraction phases, and pulse imperfections;
  • refractive-index corrections from background atoms; and
  • atomic-mass and binding-energy inputs.

The sensor-level treatment is developed in Atom-Interferometric Sensors.

For a free electron,

μe=geqe2meS,ae=∣ge∣−22.\boldsymbol\mu_e = g_e \frac{q_e}{2m_e} \mathbf S, \qquad a_e = \frac{|g_e|-2}{2}.

The Standard Model prediction can be organized as

aeSM=∑n≥1Cn(απ)n+aehad+aeweak+δaemass,a_e^{\mathrm{SM}} = \sum_{n\geq1} C_n \left( \frac{\alpha}{\pi} \right)^n + a_e^{\mathrm{had}} + a_e^{\mathrm{weak}} + \delta a_e^{\mathrm{mass}},

where the coefficients include mass-dependent QED contributions and the last terms collect hadronic, weak, and residual mass-ratio effects. A Penning-trap experiment measures the anomaly from the difference or ratio of spin-precession and cyclotron frequencies. Inverting the theoretical series gives α\alpha.

This route is extraordinarily sensitive, but it is not theory-free. The inference uses high-order QED coefficients, hadronic and electroweak contributions, and auxiliary mass ratios. Conversely, inserting an independent recoil value of α\alpha turns the electron anomaly into a stringent Standard Model test.

RouteReported inverse fine-structure constantRelative uncertaintyStatus
Cs recoil, Parker et al. (2018)137.035 999 046(27)137.035\,999\,046(27)2.0×10−102.0\times10^{-10}CODATA input
Rb recoil, Morel et al. (2020)137.035 999 206(11)137.035\,999\,206(11)8.1×10−118.1\times10^{-11}CODATA input
Electron anomaly, Fan et al. (2023) plus SM theory137.035 999 166(15)137.035\,999\,166(15)1.1×10−101.1\times10^{-10}CODATA input
CODATA 2022 adjusted value137.035 999 177(21)137.035\,999\,177(21)1.5×10−101.5\times10^{-10}Current recommendation

The caesium and rubidium recoil values differ by

Δα−1=160×10−9,\Delta\alpha^{-1} = 160\times10^{-9},

while their original combined standard uncertainty is approximately

uc=272+112×10−9≃29.2×10−9.u_c = \sqrt{27^2+11^2}\times10^{-9} \simeq 29.2\times10^{-9}.

Their pairwise separation is therefore about 5.55.5 standard deviations if the published uncertainties are treated as independent. Shared adjusted inputs make the full CODATA comparison slightly more subtle, but do not remove the experimental tension. The 2.52.5 uncertainty expansion in the 2022 adjustment is why the recommended uncertainty is larger than a naive weighted average would suggest.

The correct conclusion is not that one route has already failed. It is that the highest-precision determinations do not yet constitute a mutually consistent ensemble at their original stated uncertainties. Independent recoil geometries, atomic species, electron-anomaly measurements, and theory cross-checks remain scientifically important.

A reusable determination should separate:

  1. the primary measured quantity, such as h/mXh/m_X or aea_e;
  2. the observational equation and convention;
  3. auxiliary constants and the CODATA edition used;
  4. theory contributions and their covariance;
  5. statistical and systematic uncertainty components;
  6. correlations with earlier measurements;
  7. blind-analysis or reversal procedures; and
  8. both the direct observable and the converted α\alpha value.

Reporting only α−1\alpha^{-1} makes later re-evaluation unnecessarily difficult when a mass, theory coefficient, or recommended constant changes.

The Rydberg constant is related to the electron mass and fine-structure constant by

R∞=α2mec2h,R_\infty = \frac{\alpha^2m_ec}{2h},

or, equivalently,

hcR∞=Eh2.hcR_\infty = \frac{E_h}{2}.

It sets the leading electronic binding-energy scale for an infinitely heavy, pointlike nucleus. The subscript ∞\infty refers to the infinite-nuclear-mass limit; actual atomic levels include reduced-mass, relativistic, radiative, recoil, and finite-size corrections.

The exact identity does not make R∞R_\infty exact. In the present SI, hh and cc are exact, whereas α\alpha and mem_e are adjusted. In the CODATA inference network it is convenient to adjust R∞R_\infty using spectroscopy and connect it to other constants through observational equations.

A schematic hydrogen level can be written

Enℓj=hcR∞[fnjDirac(α,mpme)+fnℓjQED(α,mpme,…)+δℓ0CNSn3rp2+⋯].\begin{aligned} E_{n\ell j} = hcR_\infty \bigg[ & f_{nj}^{\mathrm{Dirac}} \left( \alpha,\frac{m_p}{m_e} \right) \\ & + f_{n\ell j}^{\mathrm{QED}} \left( \alpha,\frac{m_p}{m_e},\ldots \right) \\ & + \delta_{\ell0} \frac{C_{\mathrm{NS}}}{n^3}r_p^2 + \cdots \bigg]. \end{aligned}

Here fDiracf^{\mathrm{Dirac}} includes the reduced-mass relativistic spectrum, fQEDf^{\mathrm{QED}} includes radiative, recoil, hadronic, and weak contributions at the adopted order, and the displayed nuclear-size term is the leading SS-state contribution. A transition obeys

hνa→b=Eb−Ea.h\nu_{a\to b} = E_b-E_a.

At leading nonrelativistic order,

νna→nb≃cR∞(1na2−1nb2),\nu_{n_a\to n_b} \simeq cR_\infty \left( \frac{1}{n_a^2} - \frac{1}{n_b^2} \right),

but this formula is not adequate for a precision determination. The proton-radius contribution and leading Lamb-shift terms both have approximately n−3n^{-3} scaling for SS states. Consequently, one transition generally constrains a combination of R∞R_\infty, rpr_p, and QED terms rather than isolating one constant.

Two transitions with sufficiently different sensitivity vectors can determine R∞R_\infty and rpr_p under an adopted theory model. A third independent transition can then test that model. Alternatively, a precise proton radius from muonic hydrogen can be supplied as external input, allowing an electronic-hydrogen transition to determine R∞R_\infty more directly.

For transition ii, linearize around reference values:

δνi=KiR δR∞+Kir δrp2+∑kKik δqk.\delta\nu_i = K_{iR}\,\delta R_\infty + K_{ir}\,\delta r_p^2 + \sum_k K_{ik}\,\delta q_k.

The qkq_k represent additional constants or theoretical remainder parameters. If two transitions have nearly proportional rows

(KiR,Kir),\left( K_{iR},K_{ir} \right),

their combination is poorly conditioned: one direction in (R∞,rp2)(R_\infty,r_p^2) space is tightly determined and the orthogonal direction is not. The fitted constants then have a large correlation coefficient,

ρRr=cov⁡(R∞,rp2)u(R∞)u(rp2).\rho_{Rr} = \frac{ \operatorname{cov}(R_\infty,r_p^2) }{ u(R_\infty)u(r_p^2) }.

Publishing only the two marginal uncertainties hides this geometry.

Current recommendation and newer hydrogen data

Section titled “Current recommendation and newer hydrogen data”

CODATA 2022 recommends

R∞=10 973 731.568 157(12) m−1.R_\infty = 10\,973\,731.568\,157(12)\ {\rm m^{-1}}.

The adjustment expanded selected hydrogen and deuterium transition uncertainties by 1.71.7 to address their scatter.

A post-CODATA 2022 result by Maisenbacher and collaborators measured the hydrogen 2S2S–6P6P transition as

ν2S–6P=730 690 248 610.79(48) kHz.\nu_{2S\text{--}6P} = 730\,690\,248\,610.79(48)\ {\rm kHz}.

Combining it with the hydrogen 1S1S–2S2S frequency gave

rp=0.8406(15) fm,R∞=10 973 731.568 152(14) m−1,\begin{aligned} r_p &= 0.8406(15)\ {\rm fm}, \\ R_\infty &= 10\,973\,731.568\,152(14)\ {\rm m^{-1}}, \end{aligned}

with a reported correlation of approximately 0.940.94 between the inferred rpr_p and R∞R_\infty. Using the muonic-hydrogen radius as an input instead gave

R∞=10 973 731.568 1524(79) m−1.R_\infty = 10\,973\,731.568\,1524(79)\ {\rm m^{-1}}.

This latter uncertainty is smaller than the CODATA 2022 uncertainty, and the central values are compatible. The result also tests the Standard Model prediction for the measured transition at 0.70.7 parts per trillion and the relevant bound-state QED contribution at about 0.50.5 parts per million.

These are important 2026 experimental inferences, not a CODATA 2026 recommendation. The distinction matters because a global adjustment must evaluate all eligible post-cutoff data, their correlations, and any updated theory.

Hydrogen spectroscopy at this level depends on:

  • first- and second-order Doppler effects and the velocity distribution;
  • quantum-interference and line-pulling effects among nearby resonances;
  • ac and dc Stark shifts, Zeeman shifts, and blackbody radiation;
  • frequency-reference and comb traceability;
  • recoil and reduced-mass corrections;
  • proton charge and magnetic structure;
  • correlated bound-state QED remainders; and
  • the line-shape model used to map detected counts to an unperturbed frequency.

The Rydberg Formula provides the historical and leading-order spectral structure. It should not be substituted for the full observational equation in a modern constant determination.

Both

μpe=mpme\mu_{pe} = \frac{m_p}{m_e}

and its inverse

βep=memp\beta_{ep} = \frac{m_e}{m_p}

occur in the literature. The symbol μ\mu is also used for reduced mass and magnetic moment, so a precision report should define its notation explicitly. CODATA 2022 gives

mpme=1836.152 673 426(32),memp=5.446 170 214 889(94)×10−4.\begin{aligned} \frac{m_p}{m_e} &= 1836.152\,673\,426(32), \\ \frac{m_e}{m_p} &= 5.446\,170\,214\,889(94)\times10^{-4}. \end{aligned}

These are dimensionless ratios. The proton and electron masses in kilograms additionally depend on the SI realization and the atomic mass constant.

An ideal ion of mass mm and charge qq in a uniform magnetic field has free cyclotron frequency

νc=∣q∣B2πm.\nu_c = \frac{|q|B}{2\pi m}.

For two ions measured in the same field,

m1m2=∣q1∣∣q2∣νc,2νc,1.\frac{m_1}{m_2} = \frac{|q_1|}{|q_2|} \frac{\nu_{c,2}}{\nu_{c,1}}.

The magnetic field cancels only to the extent that the two frequencies sample the same field in time and space. Precision experiments alternate or simultaneously store ions, interpolate magnetic-field drift, control trap anharmonicities, and compare motional energies.

In a real Penning trap, the electrostatic potential splits the motion into modified cyclotron, axial, and magnetron modes. The Brown–Gabrielse invariance theorem gives, to first order in important trap imperfections,

νc2=ν+2+νz2+ν−2.\nu_c^2 = \nu_+^2+\nu_z^2+\nu_-^2.

The measured ion mass is not automatically the neutral-atom, nuclear, or bare-particle mass needed by an adjustment. For an ion with NeN_e remaining electrons,

mionc2=mnucleusc2+Nemec2−Ebind,m_{\mathrm{ion}}c^2 = m_{\mathrm{nucleus}}c^2 + N_em_ec^2 - E_{\mathrm{bind}},

with the sign convention that Ebind>0E_{\mathrm{bind}}>0. Electron binding energies, ionization energies, molecular dissociation energies, and their uncertainties must be applied at the precision of the mass ratio.

The electron mass is too small for the most precise direct comparison with ordinary heavy reference ions. A powerful alternative stores a hydrogenlike ion and measures both its cyclotron frequency and the Larmor frequency of its bound electron.

For ion charge qionq_{\mathrm{ion}} and mass mionm_{\mathrm{ion}},

νc=∣qion∣B2πmion,\nu_c = \frac{|q_{\mathrm{ion}}|B}{2\pi m_{\mathrm{ion}}},

while the bound-electron spin frequency is

νL=∣gbound∣eB4πme.\nu_L = \frac{|g_{\mathrm{bound}}|eB}{4\pi m_e}.

Their ratio gives

memion=∣gbound∣2e∣qion∣νcνL.\frac{m_e}{m_{\mathrm{ion}}} = \frac{|g_{\mathrm{bound}}|}{2} \frac{e}{|q_{\mathrm{ion}}|} \frac{\nu_c}{\nu_L}.

The cancellation of BB is experimental; the extraction of mem_e is theory-dependent through gboundg_{\mathrm{bound}}. That calculation includes Dirac binding, radiative, recoil, nuclear-size, and nuclear-polarization terms. Sturm and collaborators used this route with hydrogenlike 12C5+^{12}\mathrm C^{5+} to determine the electron’s relative atomic mass.

The rovibrational energies of a light molecular ion depend strongly on nuclear-to-electron mass ratios. In a Born–Oppenheimer scaling estimate,

Evib∝μnuc−1/2,Erot∝μnuc−1,E_{\mathrm{vib}} \propto \mu_{\mathrm{nuc}}^{-1/2}, \qquad E_{\mathrm{rot}} \propto \mu_{\mathrm{nuc}}^{-1},

where μnuc\mu_{\mathrm{nuc}} is an appropriate nuclear reduced mass in electron-mass units. Thus

∂ln⁡νvib∂ln⁡(mp/me)∼−12,∂ln⁡νrot∂ln⁡(mp/me)∼−1\frac{\partial\ln\nu_{\mathrm{vib}}} {\partial\ln(m_p/m_e)} \sim -\frac12, \qquad \frac{\partial\ln\nu_{\mathrm{rot}}} {\partial\ln(m_p/m_e)} \sim -1

in simple limiting models. Actual three-body calculations include nonadiabatic, relativistic, radiative, finite-size, spin, and external-field effects.

For transition ii in a molecular hydrogen ion, write

νith=cR∞Fi(mpme,mdme,rp,rd,α,…).\nu_i^{\mathrm{th}} = cR_\infty F_i \left( \frac{m_p}{m_e}, \frac{m_d}{m_e}, r_p,r_d,\alpha,\ldots \right).

The measurement constrains the parameter combination to which FiF_i is sensitive. A statement that spectroscopy “measured the proton mass” is therefore incomplete unless it specifies the other fixed or adjusted inputs and the ab initio theory covariance.

High-accuracy HD+HD^+ work has provided an independent spectroscopic route. Patra and collaborators measured a v=0→9v=0\to9 overtone with a fractional frequency uncertainty of 2.92.9 parts per trillion and inferred mp/mem_p/m_e at a fractional uncertainty of about 2121 parts per trillion. CODATA 2022 included molecular-hydrogen-ion spectroscopy in its mass adjustment.

In 2025, Alighanbari and collaborators measured an H2+\mathrm H_2^+ rovibrational transition with an 8×10−128\times10^{-12} fractional uncertainty. Their restricted least-squares analysis obtained

[mpme]H2+=1836.152 673 414(47),\left[ \frac{m_p}{m_e} \right]_{\mathrm{H_2^+}} = 1836.152\,673\,414(47),

consistent with both CODATA 2022 and the independent HD+HD^+ route. This post-CODATA result had a smaller uncertainty than the earlier bound-electron-gg-factor determination, although not smaller than the CODATA 2022 global-adjustment uncertainty.

The value is a spectroscopic inference under the adopted molecular, hydrogen, and muonic-hydrogen theory inputs. That dependence is a feature: agreement between mass spectrometry, bound-electron spin resonance, and molecular spectroscopy tests a much wider network than repeated use of one apparatus class.

Suppose three independent routes determine

mpme,mdmp,mdme.\frac{m_p}{m_e}, \qquad \frac{m_d}{m_p}, \qquad \frac{m_d}{m_e}.

They must satisfy

mdme=mdmpmpme.\frac{m_d}{m_e} = \frac{m_d}{m_p} \frac{m_p}{m_e}.

Define the logarithmic closure residual

Δcl=ln⁡ ⁣(mdme)−ln⁡ ⁣(mdmp)−ln⁡ ⁣(mpme).\Delta_{\mathrm{cl}} = \ln\!\left(\frac{m_d}{m_e}\right) - \ln\!\left(\frac{m_d}{m_p}\right) - \ln\!\left(\frac{m_p}{m_e}\right).

Its uncertainty must include cross-covariances. A statistically significant nonzero value could indicate an experimental bias, a binding energy error, an incomplete theory model, or genuinely new physics. Closure alone does not identify the cause.

The Bohr and nuclear magnetons are

μB=eℏ2me,μN=eℏ2mp.\mu_B = \frac{e\hbar}{2m_e}, \qquad \mu_N = \frac{e\hbar}{2m_p}.

They are convenient scale units, not independently adjusted particle moments. Since they contain mem_e and mpm_p, their SI values inherit mass uncertainties even though ee and hh are exact.

For angular momentum J\mathbf J, define

μ=gJμrefJℏ,HZ=−μ⋅B.\boldsymbol\mu = g_J\mu_{\mathrm{ref}} \frac{\mathbf J}{\hbar}, \qquad H_Z = -\boldsymbol\mu\mathbin{\cdot}\mathbf B.

The reference magneton and charge-sign convention must be stated. For an electron, qe=−eq_e=-e, so its magnetic moment is antiparallel to its spin for positive ∣ge∣|g_e|. CODATA tabulates the signed ratio

μeμB=−1.001 159 652 180 46(18).\frac{\mu_e}{\mu_B} = -1.001\,159\,652\,180\,46(18).

For a nucleus of spin II,

μI=gIμNIℏ.\boldsymbol\mu_I = g_I\mu_N \frac{\mathbf I}{\hbar}.

The proton has

μpμN=2.792 847 344 63(82),\frac{\mu_p}{\mu_N} = 2.792\,847\,344\,63(82),

whereas the neutron has a negative moment. Composite-particle gg factors encode internal strong-interaction structure; they are not fixed by spin alone.

Magnetic Moments and g Factors owns the general angular-momentum conventions and Zeeman Hamiltonians. Here the emphasis is their determination as constants.

For a free spin-1/21/2 particle with charge qq and mass mm,

ωL=∣g∣∣q∣B2m,ωc=∣q∣Bm.\omega_L = |g| \frac{|q|B}{2m}, \qquad \omega_c = \frac{|q|B}{m}.

Therefore,

∣g∣2=ωLωc.\frac{|g|}{2} = \frac{\omega_L}{\omega_c}.

The ratio cancels the magnetic field to first order. In a high-precision trap, however, the spin transition and motional frequencies may be measured in different trap regions or at different times. Magnetic-field drift, image-charge shifts, relativistic motional shifts, electric-field imperfections, and spin-state detection all enter the uncertainty budget.

The 2023 free-electron measurement reported

−μeμB=∣ge∣2=1.001 159 652 180 59(13).\frac{-\mu_e}{\mu_B} = \frac{|g_e|}{2} = 1.001\,159\,652\,180\,59(13).

CODATA combines it with theory and other input data rather than simply copying this number into every related entry.

For the proton, a double-trap method separates precision frequency measurement in a homogeneous field from spin-state analysis in a strong magnetic bottle. Schneider and collaborators obtained

μpμN=2.792 847 344 62(82)\frac{\mu_p}{\mu_N} = 2.792\,847\,344\,62(82)

at 0.30.3 parts per billion. The last displayed digit of the CODATA 2022 adjusted value differs because the recommendation comes from a correlated network and uses its own rounding.

A magnetic moment measured in an atom, molecule, liquid, or solid is not automatically the free-particle moment. Electronic currents shield the local field at a nucleus:

Bloc=(1−σ)Bext,\mathbf B_{\mathrm{loc}} = \left( \mathbf 1-\boldsymbol\sigma \right) \mathbf B_{\mathrm{ext}},

where σ\boldsymbol\sigma is generally a tensor. In an isotropic sample,

μ′=(1−σ)μ\mu' = \left( 1-\sigma \right)\mu

defines a shielded moment μ′\mu'. Extracting μ\mu requires a calculated or independently measured shielding correction.

A high-precision NMR ratio must therefore state:

  • the molecule or material and isotopic composition;
  • chemical state, solvent, concentration, and temperature;
  • sample shape and demagnetization convention;
  • whether the quoted quantity is free, bound, or shielded;
  • the shielding calculation and its uncertainty; and
  • correlations introduced by a common reference sample.

Labels such as “proton moment in water at 25 ∘C25\,^\circ\mathrm C” are not decorative metadata. They define the measurand.

For an SS electron, the leading Fermi-contact interaction has the form

HF∝μe⋅μI∣ψ(0)∣2.H_{\mathrm F} \propto \boldsymbol\mu_e \mathbin{\cdot} \boldsymbol\mu_I |\psi(0)|^2.

The corresponding hyperfine interval is sensitive to a product of magnetic moments and the wavefunction at the nucleus. A precision prediction also includes relativistic, radiative, recoil, nuclear magnetization-distribution, nuclear polarizability, and finite-charge-size corrections.

Consequently, hyperfine spectroscopy can determine a moment ratio only after atomic or molecular structure theory separates these contributions. For hydrogen, the Zemach radius and proton polarizability become limiting nuclear-structure terms. For many-electron atoms, electronic correlation and shielding can dominate. A precise interval is not by itself a theory-independent free nuclear moment.

Experiments often compare two moments more directly than either absolute moment:

μAμB=νAνBIAIB1−σB1−σA,\frac{\mu_A}{\mu_B} = \frac{\nu_A}{\nu_B} \frac{I_A}{I_B} \frac{1-\sigma_B}{1-\sigma_A},

schematically for two spin species in a common field. The exact equation depends on whether frequencies, angular frequencies, signs, and spin quantum numbers have been absorbed into the reported ratio.

To convert a measured shielded ratio into μA/μN\mu_A/\mu_N, an adjustment may need:

  1. another magnetic-moment ratio;
  2. one or more shielding differences;
  3. the electron-to-proton mass ratio;
  4. the electron anomaly or a bound-electron gg factor; and
  5. covariance among all these inputs.

This long conversion chain explains why CODATA magnetic-moment tables contain many correlated entries and why a local update can propagate beyond the originally measured species.

A precision spectrum becomes a constants experiment only through a forward model. For line ii,

νipred=νi(x,θ),\nu_i^{\mathrm{pred}} = \nu_i \left( \mathbf x,\boldsymbol\theta \right),

where x\mathbf x contains constants of interest and θ\boldsymbol\theta contains nuisance parameters, field shifts, line-shape parameters, and theoretical remainders. The measured line centre is

νiobs=νipred+Δiexp+ϵi.\nu_i^{\mathrm{obs}} = \nu_i^{\mathrm{pred}} + \Delta_i^{\mathrm{exp}} + \epsilon_i.

Here Δiexp\Delta_i^{\mathrm{exp}} represents applied or fitted experimental corrections and ϵi\epsilon_i the residual stochastic error under the adopted model.

The laboratory problem and the constants problem should be separated:

detector records⟶ν^i, Vν,ν^i, Vν, theory⟶x^, Vx.\begin{aligned} \text{detector records} &\longrightarrow \widehat{\nu}_i,\ V_\nu, \\ \widehat{\nu}_i,\ V_\nu,\ \text{theory} &\longrightarrow \widehat{\mathbf x},\ V_x. \end{aligned}

The first line belongs to frequency metrology and line-shape inference. The second belongs to the constants adjustment. Combining them in one opaque fit can make systematic corrections and shared theory errors difficult to audit.

For a dimensionless constant XaX_a, define

Kia=∂ln⁡νi∂ln⁡Xa.K_{ia} = \frac{\partial\ln\nu_i} {\partial\ln X_a}.

Small changes then obey

δνiνi=∑aKiaδXaXa+δνithνi.\frac{\delta\nu_i}{\nu_i} = \sum_a K_{ia} \frac{\delta X_a}{X_a} + \frac{\delta\nu_i^{\mathrm{th}}}{\nu_i}.

Sensitivity coefficients expose three distinct questions:

  • leverage: how much does the line move when a constant changes?
  • identifiability: are the sensitivity vectors of available lines linearly independent?
  • robustness: does a useful combination suppress a common nuisance or theory term?

A line with a large ∣Kia∣|K_{ia}| is not automatically the best measurement. It may be broad, field-sensitive, theoretically uncertain, or nearly degenerate with another parameter.

For a ratio Rij=νi/νjR_{ij}=\nu_i/\nu_j,

δln⁡Rij=∑a(Kia−Kja)δln⁡Xa.\delta\ln R_{ij} = \sum_a \left( K_{ia}-K_{ja} \right) \delta\ln X_a.

A common dimensional energy scale cancels when KiR=KjRK_{iR}=K_{jR}. This is why clock and molecular frequency ratios are powerful probes of dimensionless combinations. The cancellation can also reduce sensitivity to a constant one intended to determine, so the ratio must be designed for the scientific target rather than assumed to be universally superior.

An uncalculated contribution should not be hidden inside prose. One useful model introduces a theory nuisance parameter tkt_k with prior covariance VtV_t:

νith=νi,0th+∑kBiktk.\nu_i^{\mathrm{th}} = \nu_{i,0}^{\mathrm{th}} + \sum_k B_{ik}t_k.

Marginalizing over t\mathbf t contributes

Vth=BVtBTV_{\mathrm{th}} = B V_t B^{\mathsf T}

to the transition covariance. This automatically preserves shared theory errors across several lines. Treating the same omitted QED coefficient as independent noise in every transition would overstate the information content of the dataset.

Theory errors should be classified:

  • numerical convergence or basis-set uncertainty;
  • uncertainty propagated from input constants;
  • uncertainty in nuclear radii, polarizabilities, or structure;
  • truncation of a controlled perturbation series;
  • estimated uncalculated terms with shared coefficients; and
  • model discrepancy that is not justified by a probabilistic expansion.

The last category should not be assigned a tiny Gaussian uncertainty merely because the fit software requires one.

Let KK be the matrix of sensitivity coefficients and VV the total frequency covariance. The local information matrix is

I=KTV−1K.\mathcal I = K^{\mathsf T}V^{-1}K.

Small eigenvalues of I\mathcal I identify poorly constrained combinations of constants. Good experimental design can improve them by selecting:

  • transitions with complementary sensitivities;
  • isotopologues that change mass and nuclear-size dependence;
  • ratios that cancel dominant common shifts;
  • field-reversal or state-reversal channels that isolate nuisance terms;
  • direct mass or radius inputs that rotate a spectroscopic degeneracy; and
  • measurements from independent apparatus classes.

The determinant or condition number of I\mathcal I can guide design, but must be interpreted with physically meaningful parameter scaling.

A mature constants result should make the following recoverable:

ItemRequired content
MeasurandPrimary frequency, ratio, recoil quantity, anomaly, or mass ratio
ConventionSigns, charge states, magneton, isotope, free/bound/shielded status
Forward modelObservational equation and theory version
CorrectionsApplied value, sign, uncertainty, and evaluation method
CovarianceShared experimental and theoretical terms
Auxiliary inputsNumerical values, editions, and persistent references
FitParameters adjusted, priors, residuals, and goodness of fit
RobustnessReversals, subsets, alternative models, and blind-analysis status
OutputPrimary observable plus converted constant and covariance
ReusabilityData, code, or enough numerical detail for re-adjustment

The direct observable should be retained with more digits than the converted headline value. A future adjustment can then update auxiliary constants without reconstructing the experiment from a rounded plot.

Calling a derived value direct.
Atom recoil directly determines h/mXh/m_X through an apparatus model, not α\alpha without other inputs. Molecular spectroscopy directly determines a transition frequency, not mp/mem_p/m_e without molecular theory.

Using a post-cutoff paper as a new CODATA value.
A precise new result can supersede one input experimentally without superseding the internationally recommended adjustment.

Ignoring covariance.
Two constants quoted on adjacent rows of a table are not generally independent. Nor are two theory predictions that share an omitted coefficient.

Treating uncertainty expansion as agreement.
Expansion makes the adjusted uncertainty more conservative. It does not explain the source of discordant measurements.

Confusing exact and measured SI quantities.
In the current SI, hh, ee, and cc are exact; α\alpha, μ0\mu_0, and ϵ0\epsilon_0 are not.

Omitting charge and binding corrections.
A Penning trap measures an ion. Converting it to a neutral atom, nucleus, or bare particle requires mass-energy bookkeeping.

Confusing a shielded moment with a free moment.
The chemical and material environment is part of the measurand until a shielding model removes it.

Testing theory with a fitted input.
If a constant was inferred using the same theoretical relation later claimed as a test, the comparison is circular unless an independent input breaks the loop.

For any proposed determination, write the dependency graph before propagating numbers:

raw data→primary observable→corrected observable→observational equation→constant.\text{raw data} \to \text{primary observable} \to \text{corrected observable} \to \text{observational equation} \to \text{constant}.

At each arrow ask:

  1. Is it exact, calibrated, fitted, or calculated?
  2. Which uncertainty enters?
  3. Is that uncertainty shared elsewhere?
  4. Can a reversal or independent route test it?

This procedure catches many hidden assumptions before they become sub-parts-per-billion claims.

To use measurement AA as a determination and measurement BB as a test:

  1. Infer the constant from AA using theory terms independent of the one tested in BB.
  2. Propagate the full covariance into the prediction for BB.
  3. Compare the primary observable in BB with that prediction.
  4. Report the residual in physical units and normalized units.
  5. Check whether AA and BB share calibration, auxiliary data, or theory.

For example, recoil α\alpha inserted into the electron anomaly prediction tests high-order QED. Electron-anomaly α\alpha inserted back into the same anomaly formula does not.

Exercise 1: Derive the recoil observational equation

Section titled “Exercise 1: Derive the recoil observational equation”

Starting from

R∞=α2mec2h,R_\infty = \frac{\alpha^2m_ec}{2h},

derive an expression for α2\alpha^2 in terms of R∞R_\infty, h/mXh/m_X, Ar(X)A_{\mathrm r}(X), and Ar(e)A_{\mathrm r}(e). Identify which factor an atom-recoil apparatus most directly determines.

Solution

Solve the Rydberg identity for α2\alpha^2:

α2=2R∞chme.\alpha^2 = \frac{2R_\infty}{c} \frac{h}{m_e}.

Insert

hme=hmXmXme=hmXAr(X)Ar(e).\frac{h}{m_e} = \frac{h}{m_X} \frac{m_X}{m_e} = \frac{h}{m_X} \frac{A_{\mathrm r}(X)}{A_{\mathrm r}(e)}.

Therefore,

α2=2R∞cAr(X)Ar(e)hmX.\alpha^2 = \frac{2R_\infty}{c} \frac{A_{\mathrm r}(X)}{A_{\mathrm r}(e)} \frac{h}{m_X}.

The interferometric apparatus most directly determines h/mXh/m_X, after its phase, wavevector, geometry, and systematic corrections are modelled. R∞R_\infty and the relative masses are auxiliary adjusted inputs.

For 87Rb^{87}\mathrm{Rb} at wavelength λ=780 nm\lambda=780\ {\rm nm}, estimate the single-photon recoil frequency

fr=ωr2π=h2mλ2.f_r = \frac{\omega_r}{2\pi} = \frac{h}{2m\lambda^2}.

Use m≃87um\simeq87u and u=1.66054×10−27 kgu=1.66054\times10^{-27}\ {\rm kg}. Then explain why large momentum transfer is useful when frf_r is only a few kilohertz.

Solution

The atomic mass is approximately

m≃87(1.66054×10−27)=1.4447×10−25 kg.m \simeq 87(1.66054\times10^{-27}) = 1.4447\times10^{-25}\ {\rm kg}.

Hence

fr=6.62607×10−342(1.4447×10−25)(780×10−9)2≃3.77×103 Hz.\begin{aligned} f_r &= \frac{6.62607\times10^{-34}} {2(1.4447\times10^{-25})(780\times10^{-9})^2} \\ &\simeq 3.77\times10^3\ {\rm Hz}. \end{aligned}

The recoil itself is small compared with optical frequencies. Coherent transfer of many photon momenta accumulates a phase proportional to a large integer multiple of the recoil, improving statistical leverage. This does not automatically reduce wavefront, diffraction-phase, or trajectory systematics; those can also scale with the pulse sequence.

Exercise 3: Quantify the recoil discrepancy

Section titled “Exercise 3: Quantify the recoil discrepancy”

Treat the 2018 caesium and 2020 rubidium values as independent:

αCs−1=137.035 999 046(27),αRb−1=137.035 999 206(11).\begin{aligned} \alpha_{\mathrm{Cs}}^{-1} &= 137.035\,999\,046(27), \\ \alpha_{\mathrm{Rb}}^{-1} &= 137.035\,999\,206(11). \end{aligned}

Compute their difference in units of the combined standard uncertainty. What would multiplying both uncertainties by 2.52.5 do to this pairwise normalized separation?

Solution

The absolute difference is

Δ=160×10−9.\Delta = 160\times10^{-9}.

The independent combined uncertainty is

uc=272+112×10−9=29.15×10−9.u_c = \sqrt{27^2+11^2}\times10^{-9} = 29.15\times10^{-9}.

Thus

Δuc≃5.49.\frac{\Delta}{u_c} \simeq 5.49.

If both marginal uncertainties are multiplied by 2.52.5, the denominator is also multiplied by 2.52.5, giving

5.492.5≃2.20.\frac{5.49}{2.5} \simeq 2.20.

This demonstrates what uncertainty expansion does numerically. It reduces the normalized tension used by the adjustment, but it does not discover the cause or make the original experiments agree at their published uncertainties.

Consider the linearized model

(δν1δν2)=(1111+ε)(xy),\begin{pmatrix} \delta\nu_1\\ \delta\nu_2 \end{pmatrix} = \begin{pmatrix} 1 & 1\\ 1 & 1+\varepsilon \end{pmatrix} \begin{pmatrix} x\\ y \end{pmatrix},

with equal independent frequency uncertainties σ\sigma. Interpret xx as a scaled R∞R_\infty shift and yy as a scaled rp2r_p^2 shift. Solve for xx and yy. How does the uncertainty behave as ε→0\varepsilon\to0?

Solution

Subtract the two equations:

δν2−δν1=εy,\delta\nu_2-\delta\nu_1 = \varepsilon y,

so

y=δν2−δν1ε,x=δν1−y.y = \frac{\delta\nu_2-\delta\nu_1}{\varepsilon}, \qquad x = \delta\nu_1-y.

Because the two measurements are independent,

u2(y)=2σ2ε2.u^2(y) = \frac{2\sigma^2}{\varepsilon^2}.

Thus u(y)∝1/∣ε∣u(y)\propto1/|\varepsilon|, and the uncertainty of xx also diverges. At ε=0\varepsilon=0, the two sensitivity rows are identical and only x+yx+y is identifiable. The example captures why nominally precise hydrogen transitions can leave R∞R_\infty and rpr_p highly correlated.

Exercise 5: Charge states and binding energy

Section titled “Exercise 5: Charge states and binding energy”

Two ions have charges q1=5eq_1=5e and q2=eq_2=e. Their measured free-cyclotron frequency ratio is

νc,2νc,1=0.400 000 000.\frac{\nu_{c,2}}{\nu_{c,1}} = 0.400\,000\,000.

Find m1/m2m_1/m_2 in the ideal model. Then write the correction needed if ion 1 was formed from a neutral atom by removing five electrons with total ionization energy Eion>0E_{\mathrm{ion}}>0.

Solution

The ideal ratio is

m1m2=5ee(0.400 000 000)=2.000 000 000.\frac{m_1}{m_2} = \frac{5e}{e}(0.400\,000\,000) = 2.000\,000\,000.

If neutral atom 1 has mass m1,atomm_{1,\mathrm{atom}}, then

m1,ionc2=m1,atomc2−5mec2+Eion.m_{1,\mathrm{ion}}c^2 = m_{1,\mathrm{atom}}c^2 - 5m_ec^2 + E_{\mathrm{ion}}.

The positive EionE_{\mathrm{ion}} term appears because removing bound electrons requires energy: the neutral atom’s binding lowers its mass relative to the separated constituents. Therefore,

m1,atom=m1,ion+5me−Eionc2.m_{1,\mathrm{atom}} = m_{1,\mathrm{ion}} + 5m_e - \frac{E_{\mathrm{ion}}}{c^2}.

The trap ratio determines the ion mass. The electron masses and total ionization energy must be included before quoting the neutral-atom mass.

In a simple model, a vibrational transition satisfies

νvib∝(mpme)−1/2.\nu_{\mathrm{vib}} \propto \left( \frac{m_p}{m_e} \right)^{-1/2}.

If the measured frequency is 60 THz60\ {\rm THz} with a fractional uncertainty of 3×10−123\times10^{-12} and all other contributions are exact, estimate the best possible fractional uncertainty in mp/mem_p/m_e. Why is this only a lower bound for a real molecular-ion determination?

Solution

Taking logarithms gives

δln⁡νvib=−12δln⁡ ⁣(mpme).\delta\ln\nu_{\mathrm{vib}} = -\frac12 \delta\ln\!\left(\frac{m_p}{m_e}\right).

Therefore,

u(mp/me)mp/me=2u(ν)ν=6×10−12.\frac{ u(m_p/m_e) }{ m_p/m_e } = 2 \frac{u(\nu)}{\nu} = 6\times10^{-12}.

This is a lower bound because real theory also depends on R∞R_\infty, other nuclear mass ratios, charge radii, α\alpha, relativistic and QED terms, hyperfine deperturbation, and external-field corrections. Their uncertainties and correlations must be included.

A trapped electron has measured magnitude ratio

ωLωc=1.001 159 652 18.\frac{\omega_L}{\omega_c} = 1.001\,159\,652\,18.

Find ∣ge∣|g_e| and aea_e. Why is the signed ratio μe/μB\mu_e/\mu_B negative even though both numbers just calculated are positive?

Solution

Since

∣ge∣2=ωLωc,\frac{|g_e|}{2} = \frac{\omega_L}{\omega_c},

we obtain

∣ge∣=2.002 319 304 36.|g_e| = 2.002\,319\,304\,36.

The anomaly is

ae=∣ge∣−22=0.001 159 652 18.a_e = \frac{|g_e|-2}{2} = 0.001\,159\,652\,18.

The electron charge is negative. Its magnetic moment vector is therefore antiparallel to its spin vector under the common convention, so μe/μB<0\mu_e/\mu_B<0. Frequency magnitudes discard this orientation sign; recovering it requires the declared Hamiltonian and charge convention.

Let a derived quantity be

z=x−y.z=x-y.

Suppose

u(x)=2,u(y)=3,ρxy=0.8.u(x)=2,\qquad u(y)=3,\qquad \rho_{xy}=0.8.

Compute u(z)u(z). Compare with the value obtained by incorrectly assuming independence.

Solution

The covariance is

cov⁡(x,y)=ρxyu(x)u(y)=0.8(2)(3)=4.8.\operatorname{cov}(x,y) = \rho_{xy}u(x)u(y) = 0.8(2)(3) = 4.8.

For z=x−yz=x-y,

u2(z)=u2(x)+u2(y)−2cov⁡(x,y)=4+9−9.6=3.4.\begin{aligned} u^2(z) &= u^2(x)+u^2(y) - 2\operatorname{cov}(x,y) \\ &= 4+9-9.6 = 3.4. \end{aligned}

Thus

u(z)=3.4≃1.84.u(z) = \sqrt{3.4} \simeq 1.84.

Assuming independence would give

uind(z)=13≃3.61.u_{\mathrm{ind}}(z) = \sqrt{13} \simeq 3.61.

Positive correlation reduces uncertainty in a difference. For a sum, the same covariance would increase it. Dropping covariance is not automatically conservative.

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