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Photodetachment removes an electron from an anion using a photon. For chlorine, the reaction is ${\mathrm{Cl}}^{-}(g)+\gamma ⟶\mathrm{Cl}(g)+e^{-}$. Measuring the minimum photon energy for the specified final quantum state gives a photodetachment threshold and hence an electron affinity.

In the published chlorine experiment, negative ions were accelerated and mass-selected, then overlapped with a tunable laser beam. A downstream electric field deflected charged ions; neutral chemical atoms continued to a plate, whose secondary electrons were counted. Scanning the laser frequency produced an onset in this neutral-atom signal. The apparatus therefore inferred an electron affinity from a threshold, rather than measuring the heat of attachment.^[ref]

Reversing the laser direction and averaging the two thresholds corrected the first-order Doppler shift. A Fabry–Pérot interferometer and reference spectral lines calibrated the frequency. Finite laser bandwidth, unresolved quantum state splitting and shifts of the calibration lines limited the inference; the authors included these effects in fitting and the error estimate. The level diagram shows only the extracted gap, not a measured signal curve.^[ref]

A photodiode is a semiconductor diode producing photocurrent from photon absorption. Exciting an electron across the band gap leaves an electron hole. The depletion region's electric field separates the charge carriers; others can arrive by diffusion before electron-hole recombination. Contacts complete the electrical circuit.^[ref]

The useful bridge is from light to a measurable electric current: spectral responsivity converts incident radiant flux into photocurrent, while quantum efficiency counts collected signal charge carriers per incident photon. These answer different questions: how much electric current one watt produces, and how many incident photons contribute to the signal. The worked calculation below makes their relationship explicit.

A photon transfers its energy to a bound electron, ejecting it if energetically allowed. Subsequent atomic relaxation can emit characteristic radiation or additional electrons. Its material and energy dependence differs from Compton scattering, which matters when converting computed tomography attenuation to the higher photon energy of positron emission tomography.

Define $V_c$ as positive when the contact field adds to the retarding barrier, and let $V_{\mathrm{app}}$ be the signed externally imposed retarding voltage. In this chosen sign convention the barrier is $e(V_{\mathrm{app}}+V_c)$, henceThis convention specifies a model of the gap; an instrument's polarity labels must be translated into it. With a fixed $V_c$, subtraction at two frequencies removes both the work function and the offset:For an original example with the same $\Phi =2.30\mathrm{eV}$ and an additional $V_c=+0.200\mathrm{V}$, choose ${\nu }_1=6.00\times 10^{14}\mathrm{Hz}$ and ${\nu }_2=1.00\times 10^{15}\mathrm{Hz}$. The predicted terminal endpoints are $-0.018599$ and $1.635668\mathrm{V}$. The negative first endpoint calls for a small externally accelerating voltage because the contact field already over-retards the fastest electrons. Their difference is $1.654267\mathrm{V}$, giving $h/e\simeq 4.135668\times 10^{-15}\mathrm{V}\mathrm{s}$. Ignoring $V_c$ in the intercept would falsely infer $2.50\mathrm{eV}$ for the work function. The terminal line's zero would then be mistaken for a material threshold. If $V_c$ drifts between the two readings, even the slope is biased. These are calculated examples, not Millikan's measurements.

The photoelectric effect is the release of electrons from matter following photon absorption. Here the focus is emission from a metal surface into vacuum: a photon supplies energy, the work function pays the escape cost, and the remainder can become the emitted electron's kinetic energy. A photocurrent counts collected electric charge; a stopping potential probes the upper kinetic energy limit. These are different measurements.

In 1905, Albert Einstein proposed that an individual light quantum could transfer its whole energy to one electron. His §8 allowed losses before escape, distinguished the fastest emitted electrons from the rest, and predicted a straight stopping potential versus frequency relation with a material-independent slope. He separately predicted that changing light intensity changes the number emitted without changing their velocity distribution under otherwise identical conditions. He also discussed incomplete transfer and limits to the account.^[ref]

The useful modern starting model is a clean, homogeneous metal with independent single-photon events, negligible initial thermal broadening, negligible lowering of the surface barrier by an applied electric field, and negligible electric fields from the emitted electrons themselves. Specify the surface and its work function; it is not enough to name the bulk material. The Einstein photoelectric equation describes the upper edge of the emission energy distribution. It neither predicts that every absorbed photon liberates an electron nor supplies the whole photocurrent curve. Its appeal is that a complicated surface process still exposes the universal Planck constant through a simple slope.

The photoelectric saturation current is the photocurrent reached when increasing the collecting electric potential difference no longer increases the fraction of available emitted electrons collected. It is saturation with collecting voltage at fixed illumination. It does not mean that increasing incident light intensity cannot increase emission.

If $P$ is incident radiant flux on the emitting area and $\eta$ is the external quantum efficiency for producing escaping electrons, then the incident photon arrival rate is $P/(h\nu )$ and complete collection gives $I_{\mathrm{sat}}=e\eta P/(h\nu )$. For the example's $\nu =8.00\times 10^{14}\mathrm{Hz}$, choose $\eta =0.10$ and $P=1.00\mu \mathrm{W}$. The calculated photon arrival rate is $1.886488\times 10^{12}{\mathrm{s}}^{-1}$ and $I_{\mathrm{sat}}=30.224866\mathrm{nA}$. Doubling $P$ doubles this current to $60.449731\mathrm{nA}$ while leaving $V_s$ fixed. At fixed illuminated area this doubles the irradiance. Changing frequency at fixed $P$ changes the arrival rate as well as the photon energy; $\eta$ can also change, so there is no general rule that a higher frequency gives a larger photocurrent.

A missing plateau can indicate incomplete collection or an electric field altered by the emitted electric charge. Heating, surface changes and additional emission channels can invalidate a constant $\eta$. Even a small amount of unwanted higher-frequency radiation can move an apparent endpoint. A stopping potential inferred from zero net current additionally needs background subtraction and a check for emission from the collector itself.

An electron ejected following photon absorption. For a free residual ion with negligible recoil, the emitted electron's kinetic energy equals incident photon energy minus the ionization binding energy.

Let a conducting sample and conducting analyzer be in good electrical contact, unbiased, at equilibrium, and without appreciable charging during illumination. Their Fermi levels then coincide. Choose that common Fermi level as zero. Define $E_B>0$ as the binding energy relative to this zero: removing an electron into the electron reservoir at the Fermi level costs $E_B$. It is not the cost of removing the electron all the way to the sample's vacuum level.

Write the sample and analyzer work functions as ${\varphi }_s$ and ${\varphi }_a$. Their local vacuum levels lie at ${\varphi }_s$ and ${\varphi }_a$ above the common Fermi level. Conservation of energy for an electron emitted without additional losses gives total outgoing energy $h\nu -E_B$, where $h$ is the Planck constant and $\nu$ the photon frequency. Immediately outside the sample its kinetic energy is $K_s=h\nu -E_B-{\varphi }_s$. The contact-related electric potential changes this toThus the sample work function cancels when the measured kinetic energy is referenced to the analyzer. Substituting ${\varphi }_s$ for ${\varphi }_a$ in the final conversion would mix two different energy references. An instrument's calibrated binding energy scale can incorporate its effective analyzer work function, so the correction need not appear as a separate operator-entered number.

As an original numerical example, stipulate $h\nu =1486.6\mathrm{eV}$, ${\varphi }_a=4.5\mathrm{eV}$ and a line at $E_B=284.0\mathrm{eV}$. The predicted analyzer kinetic energy is $1198.1\mathrm{eV}$. If ${\varphi }_s=5.0\mathrm{eV}$, the surface value is instead $K_s=1197.6\mathrm{eV}$; the contact-related increase is $0.5\mathrm{eV}$. A second line at $286.0\mathrm{eV}$ gives $1196.1\mathrm{eV}$ at the analyzer. A $+2.0\mathrm{eV}$ chemical shift in photoelectron spectroscopy therefore appears as a $-2.0\mathrm{eV}$ shift in measured kinetic energy. These are chosen values, not a measured carbon spectrum.

Charging breaks the assumed reference. If a uniformly charging sample rises by electric potential $V>0$ relative to the analyzer, an escaping electron loses an additional energy $eV$, with $e$ the positive elementary charge. Applying the unbiased conversion consequently returnsTwo features from the same stable potential retain their separation. Features from regions at different potentials acquire different offsets, which can mimic chemical differences or broaden a line. A conducting holder alone does not establish electrical contact through an insulating surface layer. Compare repeat scans, electrical contact and charge-compensation settings before interpreting an offset as a change in chemical bonds.

Measurement calibration is a separate issue: a known reference line tests the scale, while charge compensation controls the specimen's electric potential. In an original offset model $E_{B,\mathrm{read}}=E_{B,\mathrm{true}}+b$, one known line determines $b$. An unknown scale factor in $E_{B,\mathrm{read}}=a{E}_{B,\mathrm{true}}+b$ requires two distinct known lines to determine both $a$ and $b$. Re-reading a reference after a sample checks drift. Treating an unidentified contamination peak as a universally fixed reference would assume the chemical identity and electrical behavior that the measurement should test.

Choose two hypothetical environments A and B of one chemical element, with line centers ${\mu }_A=284\mathrm{eV}$ and ${\mu }_B=286\mathrm{eV}$. Model each line by a normalized Gaussian function with common standard deviation $\sigma$, and stipulate integrated count weights $w_A=3/4$, $w_B=1/4$. On the binding energy axis $E$, the normalized count density isAll energies in this expression use electronvolts. Each component's integrated area equals its count weight, and $\int I(E)dE=1$. There is no background, statistical counting fluctuation, or additional emission feature in this stipulated model. These choices deliberately isolate photoelectron peak overlap and resolution.

Direct integration, or the law of total expectation applied to the component label, gives the centroidThe centroid lies between the chemical environments and is not either component's binding energy. Expanding $(E-\bar{E}{)}^2$ within each component, the odd cross term integrates to zero. The resulting variance isFor $\sigma =0.25\mathrm{eV}$ the variance is $0.8125{\mathrm{eV}}^2$ and the two maxima are separated. For $\sigma =1.00\mathrm{eV}$ it is $1.7500{\mathrm{eV}}^2$ and there is one maximum. Each Gaussian's full width at half maximum is $2\sqrt{2\ln 2}\sigma$, approximately $0.589$ and $2.355\mathrm{eV}$ respectively. The chemical separation remains $2\mathrm{eV}$ in both cases. The number of visible maxima therefore does not equal the number of chemical components.

One interpretation of this change is additional independent Gaussian instrument blur. The convolution of probability densities adds the variances, so broadening $\sigma =0.25$ to $1$ requires response standard deviation $\sqrt{1-0.25^2}=\sqrt{15}/4\simeq 0.968246\mathrm{eV}$. A normalized response with zero mean preserves the centroid and integrated counts. Real line shapes and backgrounds can depart from this model, and separating hidden components is an inverse problem; a plausible fit does not alone establish uniqueness.

Finally, count weights describe detection. In a simple response model, let $n_i$ denote the number of emitting sites sampled in environment $i$, $s_i$ its effective photoionization cross section, and $T_i$ the probability that its emitted electron contributes to the selected measured line. ThenThe common factor $C$ includes exposure. Here $T_i$ includes escape from the sample, analyzer transmission and detection. Count weights equal site fractions only if the relevant response factors are equal or corrected. They are not automatically molecular mole fractions; different molecules can supply different numbers of the selected emitting sites. In an original example, equal site numbers with $s_A{T}_A=3s_B{T}_B$ give the plotted $3:1$ count ratio despite a $1:1$ site ratio.

Electron optics forms a magnified spatial image of photoelectrons emitted from an illuminated surface. Emission yield and electron-energy selection can supply work-function, electronic or chemical contrast; brightness is not necessarily geometrical height.

Photoelectron spectroscopy measures the kinetic energies of photoelectrons produced by illuminating matter with photons of known energy. The photoelectric effect supplies the emission mechanism; spectroscopy turns the distribution of emitted electron energies into information about occupied energy levels and chemical bonds. A broad survey helps identify chemical elements, while small shifts within one element's lines can distinguish different chemical surroundings. These are different questions: finding carbon does not establish which chemical bonds its chemical atoms form.

The useful inversion is an energy balance. A known incoming photon energy pays for removal of an electron and for its outgoing kinetic energy. To apply that balance to a solid, specify the zero of energy and the work function of the instrument. Photoelectron binding energy reference derives the conversion for a conducting sample in electrical contact with its analyzer. A free molecule instead has an ionization energy referenced to an electron at rest in vacuum; it need not share a Fermi level with the analyzer.

electron transfer made favorable by photoexcitation of a donor or acceptor.

When the number of photoionizations equals the number of recombinations, and only those processes exchange thermal energy, equilibrium requires $⟨h\nu -h{\nu }_0{⟩}_{\mathrm{abs}}=⟨E_{\mathrm{rec}}(T)⟩$. Photon absorption and electron capture have their own spectral weights. The density cancels from this event balance, but the actual equilibrium temperature requires the two energy averages.^[ref]

A photomultiplier detects weak light by converting a photon into a photoelectron at a photosensitive cathode, then multiplying electrons through successive dynodes. Each impact can release several secondary electrons, and an anode collects the amplified packet as an electrical pulse.

If each of $m$ stages has mean multiplication $\delta$, the mean gain is approximately ${\delta }^m$. This amplification makes small signals measurable but does not eliminate photon shot noise or fluctuations in multiplication. Quantum efficiency controls the probability of producing an initial useful photoelectron, while dark current and background produce additional signals. Optical shielding, stable applied voltages and a blocked-light measurement are therefore essential to interpreting a weak-light count.^[ref]

A photon is one quantum of the electromagnetic field. In vacuum it has zero rest mass, energy $E=h\nu =\hslash \omega$, and momentum magnitude $p=E/c$. Its two physical polarization degrees of freedom are transverse to its propagation direction. A monochromatic field mode can contain zero, one or several photons; its photon number distinguishes these quantum states.

The photoelectric effect illustrates a photon's discrete energy exchange: increasing incident frequency increases the available electron kinetic energy, whereas increasing light intensity primarily increases the rate of events in the weak-illumination regime. Compton scattering additionally tests the associated momentum transfer. Interference still depends on probability amplitudes, so describing light in terms of photons does not discard its wave behavior.

For a photon incident on a stationary electron, producing an additional electron and positron leaves three massive particles in the final state. Four-momentum conservation gives $W^2=m_e^2{c}^4+2m_e{c}^2{E}_{\gamma }$ for the centre-of-momentum energy. Its minimum is $3m_e{c}^2$, so the incident threshold is $4m_e{c}^2$. At threshold all final particles are at rest in their centre-of-momentum frame, which moves at $4c/5$ relative to the target laboratory frame. This differs from a heavy-target threshold because the electron target's recoil cannot be neglected.

For a dilute ionized plasma with nonrelativistic electrons and photon energies well below $m_e{c}^2$, independent Thomson scattering events give photon survival probability $\exp (-n_e{\sigma }_{T}s)$ over proper distance $s$. Its mean gives the displayed mean free path. The scattering rate is ${\Gamma }_{\gamma }=n_e{\sigma }_{T}c$. Photons are tightly coupled when this rate greatly exceeds the Hubble parameter; photon decoupling becomes possible as the free-electron fraction falls. Frequent elastic scattering does not by itself imply chemical equilibration of the photon number.

Two photons meeting at angle $\alpha$ can produce an electron and a Positron when their combined four-momentum has sufficient invariant mass. For a head-on collision the threshold is $E_1{E}_2=m_e^2{c}^4$. Threshold means zero relative momentum in the centre-of-momentum frame, not necessarily in the laboratory.

A photon-recoil lag correlation asks how often a photon record occurs at a specified time displacement from an electron record. Let $r_e,r_{\gamma }$ be observed separate-channel rates, $S$ the rate of detected genuine pairs before a timing cut, and $f(\ell )$ their normalized timing probability density function. For an original dilute, stationary model with observation time $T$, neglecting end effects and detector dead time, the expected pair density isThis counts all pairs of records, rather than at most one detector trigger per electron. It uses independent unrelated detections for the flat term and an added same-event contribution. A normal distribution for timing spread is a chosen approximation, not a claim about the historical instrument. Intrinsic emission delay, counter response and readout uncertainty can all affect the observed probability density function.

Define the accepted lag interval by $|\ell |<w/2$: $w$ is its full width. Integrating the flat baseline gives the existing accidental coincidence expectation $T{r}_e{r}_{\gamma }w$. The additional area is $TS{\int }_{-w/2}^{w/2}f(\ell )d\ell$. Moving a window of the same full width away from the peak tests the baseline under the model's stationarity assumption. It does not remove correlated instrumental backgrounds or changing rates automatically.

For the lag model, choose $T=1000\mathrm{s}$, $r_e=2{\mathrm{s}}^{-1}$, $r_{\gamma }=0.5{\mathrm{s}}^{-1}$, $S=0.1{\mathrm{s}}^{-1}$ and timing standard deviation $\sigma =1\mathrm{ms}$. A full width $w=2\mathrm{ms}$ gives $2$ expected accidental coincidences and $100\mathrm{erf}(1/\sqrt{2})\simeq 68.27$ accepted genuine pairs, using the error function. The total is approximately $70.27$, whereas the displaced interval from $4$ to $6\mathrm{ms}$ has approximately $2.003$ expected pairs. A finite sample fluctuates around these expectations; these values are not measured counts or a significance calculation.

The right panel isolates the information lost by retaining singles totals alone. In a separate idealized model, stipulate $M=10^6$ independent $1\mathrm{ms}$ bins, with Bernoulli distribution indicators $X,Y$ for electron and photon detection in a bin. Set $p_e=\mathrm{Pr}(X=1)=0.002$ and $p_{\gamma }=\mathrm{Pr}(Y=1)=0.0005$. Independence predicts $\mathrm{Pr}(X=1,Y=1)=p_e{p}_{\gamma }=10^{-6}$, hence one expected double detection. Alternatively chooseThese nonnegative probabilities sum to one and preserve both marginal probabilities, yet predict $101$ double detections in expectation. Their covariance is $0.000101-p_e{p}_{\gamma }=0.000100$. This is an exact joint probability distribution illustrating pairing; it does not model the timing spread in the left panel or reconstruct either historical hypothesis quantitatively. Its lesson is why two singles totals cannot decide whether the observed events share a cause.