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Angle-resolved photoemission spectroscopy measures the kinetic energy and emission angle of electrons removed from a solid by light. With photon energy $h\nu$, sample work function $\Phi$, and binding energy $E_B$ measured downwards from the Fermi level, $E_{\mathrm{kin}}=h\nu -\Phi -E_B$. The measured parallel momentum is $k_{\parallel }=\sqrt{2m_e{E}_{\mathrm{kin}}}\sin \theta /\hslash$, modulo a surface reciprocal-lattice vector. Bright ridges reveal occupied electronic band structure; their slopes give the corresponding group velocity. Extracting a Fermi energy relative to a Dirac point requires a calibrated Fermi level, not merely an unlabelled image boundary.

Inverse photoemission spectroscopy injects an electron of known kinetic energy into a sample and detects the photon emitted as it enters an unoccupied electronic state. Conservation of energy, together with incident-angle information and an appropriate surface model, probes the unoccupied electronic band structure. Ordinary angle-resolved photoemission spectroscopy instead removes electrons from occupied states.

Angle-resolved photoemission spectroscopy illuminates a surface with photons of known energy and measures the kinetic energy and emission direction of the escaping electrons. Referencing the initial binding energy to the Fermi level givesHere $\Phi$ is the sample/analyser work-function reference appropriate to the calibrated energy scale, and $\theta$ is the emission angle from the surface normal. Parallel crystal momentum is conserved modulo a surface reciprocal lattice vector; measuring two angular coordinates maps the two in-plane momentum components.

Sweeping angle and energy traces the occupied spectral weight and its dispersion. In a quasi-two-dimensional sheet, no detailed free-electron model of the perpendicular final-state momentum is required to map the in-plane bands. Peaks reflect the occupied single-particle spectral function, multiplied by Fermi occupation and photoemission matrix elements and broadened by finite lifetimes and resolution. Ordinary photoemission does not directly measure empty conduction bands; a gap may need complementary information. A clean surface, vacuum and charge control are especially important for an insulating specimen.

Ultraviolet photoelectron spectroscopy probes occupied valence states through photoemitted electron energies. Angle-resolved photoemission spectroscopy adds emission direction and therefore parallel crystal momentum, revealing occupied band dispersions and Fermi contours. For a clean periodic surface, $k_{\parallel }=\sqrt{2m_e{E}_{\mathrm{kin}}}\sin \theta /\hslash$ modulo a surface reciprocal-lattice vector. A two-dimensional surface band has no intrinsic perpendicular dispersion; varying photon energy helps distinguish it from bulk bands, while allowing for matrix-element changes. A simple surface-state example is a parabolic band $E({\mathbf{k}}_{\parallel })=E_0+{\hslash }^2{k}_{\parallel }^2/(2m_{\ast })$.

Scanning tunneling spectroscopy measures local differential conductance. With a suitable featureless tip and weak tunneling, $dI/dV$ samples the local density of states, giving occupied and unoccupied features on opposite bias sides. It provides spatial localization, defects and standing-wave patterns, while ordinary spectroscopy at one point does not directly give the complete momentum-resolved band structure. For the parabolic two-dimensional band, the ideal density of states has a step at its onset, while spatial interference can supply information about allowed wavevectors. Inverse photoemission spectroscopy accesses unoccupied states by injecting electrons and measuring emitted photons. Optical absorption and electron energy loss spectroscopy instead probe allowed excitation energies and collective modes, with their own selection rules and momentum ranges. These methods supply complementary information; none automatically returns the full interacting band structure without matrix elements, resolution and surface effects.

For the Pt core-level spectra, electrons suffering inelastic losses emerge with reduced kinetic energy and appear at larger inferred binding energies. Loss tails and secondary-electron contributions therefore generate the background, principally on the high-binding-energy side of a core peak. The two clean-surface components correspond to different environments of the same Pt core-level branch. The stated values imply a surface core-level shiftReduced coordination at a surface narrows the $d$ band. In a simple almost-filled-band picture, maintaining its occupation moves the band center upward relative to the Fermi level; associated local-potential changes can move core levels upward too, reducing their binding energy. This is a plausible initial-state explanation of the negative shift. Final-state screening of the core hole also matters, so the measured shift alone does not uniquely determine a local charge or separate these mechanisms.

After adsorption, Pt atoms directly bonded to CO have a different local potential, hybridization and core-hole screening. In carbon monoxide adsorption on platinum, carbon-end donation and metal-to-molecule back-donation change the Pt–CO bond and hence the Pt core binding energy. The additional weak high-binding-energy component is naturally assigned to these chemically modified surface Pt atoms. Its small weight is compatible with only a minority of surface sites being occupied; a quantitative coverage estimate requires fitted areas and appropriate attenuation assumptions.

The new component is centered at approximately $71.9$–$72.0\mathrm{eV}$ in the supplied plot. Relative to bare surface Pt at $70.5\mathrm{eV}$, the core-level chemical shift is thereforeUsing the bulk peak as the reference would instead give about $+1.0$–$1.1\mathrm{eV}$, which answers a different comparison. The plotted axis runs toward decreasing binding energy to the right, so the additional peak on its left is a positive binding-energy shift. The estimate is a graphical reading, with no claim to sub-tenth-eV precision or a unique charge-transfer value.

Angle-resolved photoemission spectroscopy maps occupied energy bands: ultraviolet or x-ray photons eject electrons, and an energy- and angle-resolving analyzer measures $E_{\mathrm{kin}}$ and emission direction. The photoelectric effect gives the binding energy $E_B=h\nu -\Phi -E_{\mathrm{kin}}$; the parallel momentum follows from $k_{\parallel }=\sqrt{2m{E}_{\mathrm{kin}}}\sin \theta /\hslash$, up to surface reciprocal vectors. Clean surfaces and controlled photon energy are needed, and an occupied-state measurement alone does not map an empty conduction band.

Scanning tunneling spectroscopy instead brings a conducting tip close to a surface and modulates the bias while recording the differential tunnel current. At low temperature with a smooth tip density of states and tunnelling matrix element, $dI/dV$ probes the local density of states near energy $E_F+eV$. The signal is thermally broadened and depends on tunnelling selection, so it is not an unqualified map of the whole bulk band structure.

Bulk probes complement these surface measurements. In the de Haas-van Alphen effect, a low-temperature magnetization or torque measurement versus magnetic field gives quantum-oscillation frequencies $F=\hslash A_{\mathrm{ext}}/(2\pi e)$, measuring extremal Fermi surface sections; temperature damping gives a cyclotron effective mass. The linear electronic heat capacity gives the density of low-energy excitations at the Fermi level. Optical absorption measures transition thresholds and matrix-element-weighted joint densities, rather than a unique full dispersion by itself.

Different measurements reveal different aspects of electronic band structure; a convincing determination combines their constraints.

Angle-resolved photoemission. In angle-resolved photoemission spectroscopy, photons of known energy eject occupied electrons. Measuring their kinetic energy and emission angle reconstructs binding energy and the component of crystal momentum parallel to the surface:Here $\Phi$ is the sample work function when kinetic energy is referenced to the nearby vacuum; an analyzer energy scale requires its own work-function calibration. Momentum is conserved modulo a surface reciprocal lattice vector, neglecting photon momentum. Tracking the peaks maps occupied dispersion relations and the Fermi surface. The measured intensity also contains the matrix element, the Fermi-Dirac distribution and the spectral function, so an absent bright feature does not establish an absent band. For a three-dimensional solid, the perpendicular momentum requires a final-state model. Inverse photoemission spectroscopy probes unoccupied states by injecting electrons and detecting emitted photons.

Optical spectroscopy. Photon absorption and ellipsometry measure interband transitions, optical selection rules and the complex dielectric response. Because optical photon momentum is small on the scale of the Brillouin zone, direct transitions approximately preserve crystal momentum. Their onset constrains a direct band gap; a threshold involving a phonon can reveal an indirect band gap. Peak positions constrain energy differences between bands, but the response also depends on the joint density of states and optical matrix elements, so it does not uniquely determine every $E_n(\mathbf{k})$.

Quantum oscillations and cyclotron resonance. In clean samples at low temperature, the de Haas-van Alphen effect measures oscillations in magnetization and the Shubnikov-de Haas effect measures oscillations in electrical resistivity as the inverse magnetic field is varied. Their period in inverse magnetic field is $1/F$, where Onsager quantization relates $F$ to an extremal Fermi-surface area perpendicular to the field:Rotating the magnetic field maps the geometry of extremal orbits. The thermal damping determines the cyclotron effective mass,with the appropriate magnitude for a hole orbit. Cyclotron resonance supplies the corresponding dynamical mass through ${\omega }_c=eB/m_c$. These are detailed probes near the Fermi level, rather than measurements of all occupied bands. Diffraction supplies the reciprocal lattice needed to label the measured momenta, but diffraction by itself is not a measurement of electronic dispersion.

Energy and momentum measurement. In angle-resolved photoemission spectroscopy, monochromatic photons illuminate a clean surface in vacuum, and an electron energy analyzer measures the outgoing kinetic energies and emission directions. Measuring both gives the occupied electronic band structure, rather than only a momentum-integrated distribution of removal energies.

Choose a common energy reference for initial and final states. Let $E_i$ be the initial electron energy, $E_F$ the Fermi energy, and $E_{\mathrm{vac}}=E_F+\varphi$ the vacuum level immediately outside the sample. The binding energy is $E_B=E_F-E_i\ge 0$. For a direct emission event without additional losses, conservation of energy givesHere the work function $\varphi$ is the energy from the Fermi level to the local vacuum. The initial and final energies are total single-electron energies on the same scale, while $E_{\mathrm{kin}}$ is measured above vacuum. The diagram illustrates each interval independently.

Neglecting ultraviolet photon momentum, photoemission momentum conversion giveswhere $\theta$ is measured from the surface normal. Parallel crystal momentum is conserved modulo a surface reciprocal lattice vector; the surface breaks perpendicular translation symmetry. A three-dimensional sample therefore generally needs a final-state model to infer perpendicular momentum. The stated two-dimensional sheet avoids that ambiguity. The kinetic energy used in this formula is the sample-vacuum value; if the analyzer and sample have different work functions, their contact potential must be included when converting the analyzer's reading, as in photoelectron binding energy reference.

Spectral information. Define $ϵ=E_i-E_F=-E_B$ and the electron spectral function by $A(\mathbf{k},ϵ)=-\mathrm{Im}{G}^R(\mathbf{k},ϵ)/\pi$. In the sudden approximation, the basic photoemission intensity and spectral function relation isbefore instrumental broadening and background are included. Here $f$ is the Fermi-Dirac distribution, and $\mathcal{M}$ is the transition matrix element. The electron removal spectral function contains the occupied part of the spectrum. In a noninteracting band it has a delta peak at the band energy; interactions shift and broaden peaks and can add incoherent weight. Thus peak trajectories reveal dispersion, while line shapes can constrain lifetimes after resolution effects are accounted for. Dividing by known matrix and occupation factors can estimate $A$ where those factors are appreciable; intensity alone is not identical to $A$, and a missing peak can reflect a matrix-element suppression. States well above $E_F$ are not accessible to ordinary low-temperature photoemission.

Two independent band-structure probes. First, the de Haas-van Alphen effect measures oscillatory magnetization as Landau levels cross the Fermi level when a magnetic field changes. The inverse-field frequency iswhere $S_{\mathrm{ext}}$ is an extremal Fermi surface cross-sectional area perpendicular to the field. Changing field orientation maps its shape. This reveals the momentum-space geometry of occupied bands; the related Shubnikov-de Haas effect measures oscillatory resistance.

Second, absorption or reflectance spectroscopy detects interband transitions. Photon energies at absorption edges and peaks constrain the band gap and interband energy differences. For a direct band gap, negligible photon momentum selects approximately vertical transitions in the band diagram, weighted by the joint density of states and transition matrix elements. An indirect transition needs a phonon to carry the extra crystal momentum. These measurements provide evidence beyond a free-electron parabola, although an optical spectrum alone does not reconstruct every band's dispersion.

Reading the graphite spectra. For each direction, follow a moving peak through successive angles and convert each peak's own kinetic energy to $k_{\parallel }$; angle is not itself proportional to momentum over this wide range. The prominent dispersing valence feature starts at roughly $7$–$9\mathrm{eV}$ binding energy near $\Gamma$ and moves towards lower binding energy as $k_{\parallel }$ increases. Along $\Gamma K$ it approaches the Fermi level at the corner, then turns back to larger binding energy on continuing beyond the corner. Along $\Gamma M$ it reaches a finite minimum binding energy of roughly $3$–$4\mathrm{eV}$ near the edge midpoint and turns back; it does not reach the Fermi level there. Additional deeper peaks describe other occupied valence branches, with visibility varying across the spectra.

A useful qualitative description is the upper occupied $\pi$ band of the nearest-neighbour model of graphene: $E_{\pi }=-t|f(\mathbf{k})|$. It rises from $-3t$ at $\Gamma$ to zero at $K$, but only to $-t$ at $M$. The schematic curve in the figure captures those two different behaviours. It is not a full multi-orbital assignment or a quantitative fit to graphite, whose deeper valence features are also visible in the supplied spectra.

Angle needed to reach the corner. The corner's parallel wavevector isUse the near-zero binding energy of the upper valence band at that point. With the sample work function interpreted as the stated $3.8\mathrm{eV}$ separation below vacuum,HenceThe energy and angle readings in the PDF are approximate. If a peak at the corner were instead assigned a small binding energy $E_B$, the estimate becomesFor $E_B=0$–$1\mathrm{eV}$ this gives about $57$–$60^{\circ }$, consistent with the near-Fermi feature in that angular range. Substituting the full photon energy for the kinetic energy would omit the work-function cost and underestimate the required angle.

An angle-resolved photoemission spectroscopy intensity map locates occupied electronic band structure through its bright dispersing ridges. For a nearly isotropic graphene cone,Fit straight lines to the reasonably linear portions of the ridges, avoiding the broad central crossing, and extrapolate them to locate the Dirac point energy $E_D$. The PDF places the crossing near $k_y=0$ and plotted energy roughly $1.4$–$1.5\mathrm{eV}$. On a lower branch, a representative change from approximately $(|k_y|,E)=(0.10{\mathring{\mathrm{A}}}^{-1},0.9\mathrm{eV})$ towards $(0,1.5\mathrm{eV})$ gives a slope near $6\mathrm{eV}\mathring{\mathrm{A}}$. Allowing for the ridge width gives about $5$–$7\mathrm{eV}\mathring{\mathrm{A}}$, henceHere $1\mathrm{eV}\mathring{\mathrm{A}}/\hslash =1.52\times 10^5\mathrm{m}{\mathrm{s}}^{-1}$.

To determine the carrier Fermi energy, identify the Fermi level from a calibrated photoemission cutoff, then measure its separation from the Dirac point:The separation of the two Fermi crossings gives $2k_F$ for a cut through the cone centre. This determines the doping energy relative to the Dirac point; the absolute plotted energy origin is not itself a Fermi energy.

The reproduced panel has no marked Fermi level or stated energy-zero calibration. Its upper ridges end near $1.9\mathrm{eV}$, but that alone does not prove that the endpoint is a Fermi cutoff. If it is the intended cutoff, the estimate is $E_F^{\mathrm{cone}}\simeq 0.4$–$0.5\mathrm{eV}$ and $k_F\sim 0.06$–$0.08{\mathring{\mathrm{A}}}^{-1}$. If instead the plotted numbers are binding energies measured from an unstated Fermi zero, the inferred separation would be roughly $1.4$–$1.5\mathrm{eV}$. The supplied figure securely supports the slope estimate, but it does not distinguish these energy-reference conventions; an unconditional numerical Fermi energy requires the missing calibration.

Within the dipole and sudden approximation, angle-resolved photoemission spectroscopy measures the electron removal spectral function multiplied by a transition matrix element. Finite instrumental energy and angular resolution convolve this product, and inelastic scattering adds a background. Peak positions reveal occupied electronic band structure, while intrinsic line widths contain lifetime information. Matrix elements depend on photon energy, polarization, orbital character, and geometry, so weak intensity does not by itself establish the absence of an electronic state. Equilibrium photoemission does not directly measure unoccupied bands far above the Fermi level.