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The Bragg angle is the glancing angle from the incident beam to the selected lattice planes, with $0<\theta \le 90^{\circ }$. If $\alpha$ is instead the angle from the beam to the plane normal, $\alpha =90^{\circ }-\theta$ and Bragg's law becomes $n\lambda =2d\cos \alpha$. Defining the angle explicitly prevents a sine-versus-cosine error as well as a factor-of-two error in the detector deflection.

Choose $\lambda =0.154\mathrm{nm}$ and $d=0.200\mathrm{nm}$ as an illustrative model, not historical measurements. For the first diffraction order,The second diffraction order has $\sin \theta =0.770$ and $2\theta \simeq 100.707778^{\circ }$; the third would require $\sin \theta =1.155$ and is impossible. These are different diffraction orders of the same interplanar spacing at the same wavelength.

Conversely, a first-order reflection at a measured deflection $2\theta$ gives the interplanar spacingUsing $2\theta \simeq 45.287481^{\circ }$ recovers $d\simeq 0.200\mathrm{nm}$. This is the useful reversal: a known wavelength turns an angular measurement into an atomic length. An unassigned diffraction order or an unknown wavelength prevents that single measurement from determining $d$ uniquely.

William Lawrence Bragg introduced the plane interpretation; his father William Henry Bragg built the X-ray spectrometer. Their joint 1913 paper, The Reflection of X-rays by Crystals, reports the experiment. ^{[ref] [ref]}

An X-ray tube supplied radiation through lead slits to a crystal mounted with its cleavage face through the rotation axis. A rotating ionization chamber replaced a spectrometer telescope; electric current measured the scattered signal, and a circular scale supplied angular readings. They first scanned the chamber at fixed crystal orientation, then swept crystal and chamber together to follow the reflection. ^[ref]

Changing chamber gas checked detector dependence; readings on opposite sides checked face-setting errors. Repeated peaks with sines of half-deflections in integer ratios, together with matching absorption coefficients, distinguished repeated diffraction orders of the same wavelength from different radiation components. Comparing crystal faces constrained interplanar spacings. Their limits included slit broadening, face alignment and incomplete interception at glancing incidence; assigning absolute wavelengths still required a structural choice for $d$. ^[ref]

Bragg's law selects directions of constructive interference in coherent elastic scattering from equally spaced lattice planes:Here $d>0$ is the perpendicular interplanar spacing, $\lambda >0$ the incident wavelength, $n$ the positive integer diffraction order, and $\theta$ the Bragg angle, measured between the incoming beam and the lattice planes. The scattering deflection, between incoming and outgoing propagation directions, is $2\theta$. Thus a plotted detector angle $2\theta$ must be halved before insertion into Bragg's law. The $\theta$ in the parent elastic Bragg scattering condition denotes the full deflection; the present $\theta$ denotes half of it. ^[ref]

The lattice planes organize wave interference throughout a crystal structure; they are not literal metal mirrors or separate reflecting surfaces. The picture assumes elastic scattering, hence an unchanged wavelength, and sufficiently stable relative wave phases across the contributing lattice planes. X-ray wavelengths comparable with atomic interplanar spacings make these directions experimentally accessible. The sine cannot exceed one: an order exists geometrically only if $n\lambda /(2d)\le 1$. For $\lambda >2d$, even the first diffraction order is inaccessible. A geometrically possible direction need not have nonzero wave intensity; the crystal lattice structure factor and crystal basis structure factor also matter. ^[ref]

A crystal structure specifies the chemical species and spatial arrangement of the chemical atoms or ions in a crystal. For an ideal periodic structure, separate two ingredients: a Bravais lattice specifies the translations that repeat the arrangement, and an atomic basis of a crystal specifies the chemical motif repeated at every lattice point. The outward shape, or crystal habit, is a different description: the internal arrangement is what this article describes.

For a concrete two-dimensional model, choose primitive lattice translation vectors $a_1=(2,0)$ and $a_2=(0,1.5)$ in arbitrary length units. At every lattice point $R=m{a}_1+n{a}_2$, with integers $m,n$, place species A at $R$ and a different species B at $R+(0.65,0.55)$. Translating by $a_1$ or $a_2$ preserves both the positions and their chemical labels. Translating by $(0.65,0.55)$ sends one A position to a B position, so it is not a translation symmetry of the labeled structure. A picture of dots with the labels erased can therefore conceal essential chemical information.

A primitive unit cell contains one lattice point, but may contain several chemical atoms. A conventional unit cell can contain several lattice points to display the symmetry more clearly. Thus the conventional cube of a face-centered cubic lattice contains four lattice points, whereas a body-centered cubic lattice has two. Neither lattice name alone specifies which chemical species occupies the repeated motif. The NaCl conventional cell and coordination example makes the distinction explicit.

This separation is useful experimentally: interplanar spacings constrain the repeating geometry, while relative wave intensities also depend on the atomic basis of a crystal through the crystal basis structure factor. The Bragg crystal reflection experiment of 1913 describes the X-ray spectrometer, angular scans and detector checks in detail. Its conversion from angle to length is developed under Bragg's law; a geometrically possible reflection can still have zero wave intensity.

William Lawrence Bragg's 1913 structure determination supplied a complementary test. He directed X-rays through sodium chloride sections cut parallel to a cube face and recorded spots on photographic plates. Comparing section thicknesses tested how transmission altered the pattern: the relative spot strengths changed. Comparing related salts led him to two interpenetrating face-centered cubic lattices, one for each kind of constituent. He explicitly distinguished evidence for that arrangement from the still-needed identification of a single chemical atom with each scattering center. The photographs were evidence for a structural model, not direct pictures of labeled ions.^[ref]

A crystal X-ray spectrometer selects a narrow wavelength interval by diffraction at known interplanar spacing $d$ and Bragg angle $\theta$. For fixed diffraction order $n$, a known $d$ lets an angular measurement determine $\lambda =2d\sin \theta /n$. This reverses the crystallography problem of finding $d$ from a known wavelength.

Siegbahn's laboratory developed X-ray tubes and evacuated spectrographs for longer wavelengths. Rotating the crystal selected reflections; photographic plates recorded positions. Opposite-side exposures measured angles on both sides of the direct beam. Later tube instruments mounted a beam-defining slit opposite the plate holder. A separate double instrument compared two reflected beams with two ionization chambers. These were different instruments, not one universal assembly.^[ref]

The Nobel biography describes constant-temperature spectrographs and a precision angular scale read by diametrically opposed microscopes.^[ref] Temperature control matters because thermal expansion changes $d$; an accurately read angle cannot compensate for an unknown interplanar spacing.

The schematic separates preparation, selection and readout. An X-ray tube target supplies Characteristic X-rays with a possible bremsstrahlung background. A collimator limits incident directions; evacuation reduces air X-ray attenuation. Rotating the crystal brings different wavelengths into reflection. A photographic plate stores line positions over an exposure, whereas an ionization chamber can measure collected electric charge at successive angles. Neither readout alone establishes absolute wavelength: an angular zero, angular-scale calibration, diffraction order, $d$ and any required refraction correction enter the inference. Narrower slits reduce accepted angular spread but also reduce signal; a weak line can become harder to locate despite a narrower instrumental response.

A control reported in Siegbahn's lecture photographed a line system with copper-sulphate and calcium-sulphate crystals. Irregular relative shifts around copper's characteristic frequency supported anomalous dispersion; the arrangement excluded differing absorption across that frequency as the explanation.^[ref] A finer angular scale alone cannot remove this physical refraction correction.

A spectral doublet comprises two neighbouring spectral lines. Resolving it requires information about the line response, relative strengths and noise, not only precision in reading an angle. Choose two equal angular responses shaped as Gaussian functions with common standard deviation $\sigma$ and separation $\Delta$. If $x$ is angular displacement from their midpoint, their summed signal isThese are assumed response shapes, not a measured Siegbahn frequency spectrum. By symmetry $f^{\prime }(0)=0$, andThe midpoint changes from a maximum to a minimum at $\Delta =2\sigma$. For this particular equal-width, equal-height model, two distinct maxima occur when $\Delta >2\sigma$. Each isolated Gaussian function has full width at half maximum $2\sqrt{2\ln 2}\sigma \simeq 2.355\sigma$; the two-maxima threshold is therefore about $0.849$ times that width.

In this chosen model, the two Bragg angles are $30.000000^{\circ }$ and $30.033085^{\circ }$. Their separation is $0.827$ times $\sigma$ for $\sigma =0.040^{\circ }$, giving one maximum, and $4.136$ times $\sigma$ for $\sigma =0.008^{\circ }$, giving two. Sharpening the response can reveal the doublet without changing either emitted wavelength.

The Rayleigh criterion uses a first-zero convention for specified diffraction patterns. A Gaussian function has no finite zero, so its two-maxima threshold is not the Rayleigh criterion. Neither convention is a universal inference limit: known response shapes and adequate signal-to-noise ratio can support estimating a separation before two visible maxima appear. Unequal strengths, background, finite sampling and uncertainty in the response can make that inference much harder. Measurement resolution, the precision of an isolated line's centre and absolute wavelength accuracy should therefore be reported separately.

The interplanar spacing $d$ is the perpendicular distance between parallel planes in a specified family. Measuring along an oblique line gives a larger distance, so the direction of measurement matters.

There is a short reciprocal lattice derivation. With the angular convention $a_i\cdot b_j=2\pi {\delta }_{ij}$, put $G=h{b}_1+k{b}_2+l{b}_3$. Then $G\cdot r=2\pi m$ is the same plane equation as $hx+ky+lz=m$. Thus $G$ is a normal vector. Moving between consecutive sheets along this normal changes the dot product by $2\pi$, givingFor perpendicular cubic axes of length $a$, this becomesFor example, choose a primitive cubic lattice with $a=0.600\mathrm{nm}$. Its $(210)$ lattice planes have $d_{210}=0.600/\sqrt{5}\simeq 0.268328\mathrm{nm}$. This is a chosen geometry, not an experimental value. The distance from a point to a plane gives the same result: the planes $2X+Y=0$ and $2X+Y=a$ in ordinary Cartesian length coordinates are separated by $a/\sqrt{5}$.

Specify whether $d_{hkl}$ denotes spacing between successive occupied lattice planes or the formal spacing assigned to a reflection label. In a primitive cubic lattice, $(200)$ has formal spacing $a/2$ but every other sheet contains no lattice points; its reflection is the second diffraction order of $(100)$. In a face-centered cubic lattice with conventional cubic axes, the $(200)$ sheets at half-integer $X/a$ do contain lattice points. Here $a/2$ is the actual spacing of the complete family perpendicular to that cube edge. The Primitive cubic Bragg peak positions example explains how to avoid counting a reflection twice.

Choose an original simulated model: a primitive cubic lattice with one identical point scatterer per primitive unit cell, edge $a=0.400\mathrm{nm}$, and incident X-ray wavelength $\lambda =0.200\mathrm{nm}$. These are stipulated lengths, not measurements of sodium chloride. Suppose orientation information has already assigned the two observed reflections the Miller indices $(100)$ and $(110)$. The detector deflection is $2\theta$, where $\theta$ is the Bragg angle.

Use the existing interplanar spacing formula and Bragg's law, with higher diffraction orders absorbed into the reflection indices:The simulated $(100)$ reflection has $\sin \theta =1/4$, hence $2\theta =28.9550^{\circ }$. The $(110)$ reflection has $\sin \theta =\sqrt{2}/4$, hence $2\theta =41.4096^{\circ }$. Their squared sines are $0.0625$ and $0.125$, in ratio $1:2$. Substituting the unrounded angles independently givesAgreement tests a proposed indexing and scale together; disagreement would prompt checks of the indexing, wavelength, angular zero, or the assumed unit cell geometry.

Two peak positions alone do not establish the indexing. Assigning the same two angles to $(110)$ and $(200)$ would give $N=2,4$ and $a=0.400\sqrt{2}\simeq 0.565685\mathrm{nm}$ instead. More reflections, orientation information and systematic absences help discriminate such assignments. An unobserved reflection can be inaccessible, weak or extinguished by the atomic basis; absence is not automatically evidence for a larger interplanar spacing.

Absolute scale also requires measurement calibration of the wavelength. To first order, differentiation of the inferred length giveswith angular changes in radians. A stipulated detector-zero error $\delta (2\theta )=+0.100^{\circ }$, with correct wavelength, biases the first inferred edge downward by approximately $0.338\%$ and the second by $0.231\%$. A common angular offset therefore need not cancel when two inferred lengths are compared. These are model sensitivity estimates, not historical instrument uncertainties.

In neutron diffraction, coherent elastic scattering adds scattering amplitudes from regularly positioned scatterers. Since $E_f=E_i$, the neutron scattering kinematics gives $k_f=k_i=2\pi /\lambda$ andFor lattice planes of interplanar spacing $d_{\mathrm{p}}$, constructive addition requires $Q=2\pi n/d_{\mathrm{p}}$ along the plane normal. Equating these expressions proves Bragg's law:For example, stipulate $d_{\mathrm{p}}=2$ ångströms and $\lambda =2$ ångströms. The first diffraction order has $\theta =30^{\circ }$ and detector deflection $60^{\circ }$. A peak position constrains a period; its intensity also depends on the crystal basis structure factor.

Clifford Glenwood Shull describes powdered sodium chloride, a crystal monochromator, and a shielded counter recording angular counts. Inserting cadmium measured background; substantial diffuse scattering complicated peak interpretation.^[ref]

Powdering supplies many crystal orientations. Comparing the angular peaks with Bragg's law constrains crystal structure; a background estimate helps distinguish specimen peaks from unwanted counts. A two-axis diffraction instrument has no separate outgoing energy analysis, so an angular pattern alone does not separate every inelastic contribution. The richer magnetic example, including a warm/cold comparison and its limits, is the manganese monoxide neutron diffraction experiment. Its extra peaks reveal magnetic order beyond the chemical periodicity; the associated magnetic neutron diffraction model is developed there.

Consider a chosen primitive cubic lattice $a{\mathbb{Z}}^3$ with $a=0.400\mathrm{nm}$ and one identical point scatterer per primitive unit cell. Retain the incident wavelength $\lambda =0.154\mathrm{nm}$. This is an ideal point model. Its reciprocal lattice vectors are $q=(2\pi /a)(h,k,l)$ for integer triples other than $(0,0,0)$. Write $S=h^2+k^2+l^2$. The associated interplanar spacing and first-order Bragg angle satisfyThe reflection labels $(hkl)$ use the Miller index convention, keeping unreduced triples to encode diffraction order. With that convention, set $n=1$ in Bragg's law for each label. The $(200)$ reflection is equivalently the second diffraction order of $(100)$: $d_{200}=a/2$ does not imply extra scatterers halfway between the occupied $(100)$ planes. Counting both descriptions as distinct reflections would count the same direction twice.

For $(100)$, $(110)$, $(111)$ and $(200)$, respectively, $S=1,2,3,4$ and the calculated interplanar spacings are $0.400000$, $0.282843$, $0.230940$ and $0.200000\mathrm{nm}$. Their calculated deflections $2\theta$ are $22.197435^{\circ }$, $31.594744^{\circ }$, $38.952948^{\circ }$ and $45.287481^{\circ }$. Equal steps in $S$ give equal steps in ${\sin }^2\theta$, not equal steps in $2\theta$. This regularity makes an angular pattern a test of a proposed crystal structure.

A real crystal structure has a Bravais lattice together with an atomic basis of a crystal. The crystal lattice structure factor selects the periodic directions; the crystal basis structure factor combines the scattering amplitudes of atoms within a unit cell and can cancel a reflection. Consequently Bragg's law alone predicts neither allowed reflections nor their wave intensities. ^[ref] Systematic absences further restrict observed families; for example, face-centered cubic lattice centering permits only indices all even or all odd in conventional cubic indexing. The four strips above apply to the stated primitive cubic lattice, not to sodium chloride or a face-centered cubic lattice. ^[ref]

For two lines measured with the same interplanar spacing at the same temperature, division of Bragg's law givesThe common $d$ cancels. Consequently a precise wavelength ratio can coexist with an uncertain conversion to SI length. In contrast, angular calibration errors generally survive: a shared small zero offset $ϵ$ changes the inferred ratio fractionally by approximately $(\cot {\theta }_1-\cot {\theta }_2)ϵ$. Nearby lines partially cancel this effect, but widely separated angles need not. Different crystals, temperatures or refraction corrections also prevent unqualified cancellation.

Choose a one-dimensional crystal with cell translation $a$ and two atoms per cell at $0$ and $d=a/2$. Here $d$ is an intracell displacement, distinct from the interplanar spacing $d_{\mathrm{p}}$ above. In a single-scattering approximation, a row of $N$ cells has scattering amplitudeThe sum selects reciprocal lattice positions $Q_h=2\pi h/a$ as $N$ becomes large. At these positions, the two-site crystal basis structure factor and its squared magnitude areConsequently $b_1=b_2=b$ gives even reflections of strength $4b^2$ and extinguishes the odd reflections. Choosing $b_1=b$, $b_2=b/2$ instead gives $9b^2/4$ and $b^2/4$: the odd/even ratio is $1/9$. Equal atomic numbers would not establish equal $b_j$ if the isotopes differ. The figure below plots these chosen coefficients, without assigning them to actual elements. Missing reflections can encode destructive wave interference within a cell, not the absence of matter at a site.

X-ray crystallographic structure inference is an inverse problem: infer a crystal structure from measured X-ray diffraction. A proposed unit cell and atomic basis of a crystal predict a pattern; structure determination asks which proposals survive comparison with that pattern. The useful separation is between directions and strengths. Peak positions constrain the reciprocal lattice and hence interplanar spacings; relative wave intensities constrain the motif through the crystal basis structure factor. Knowing a repeat distance does not locate all the chemical atoms within that repeat.

The lattice constant from two indexed reflections example isolates the geometric inference. Basis intensities and phase ambiguity then holds the translations fixed while changing the motif. Even complete, noiseless wave intensity data need not determine all wave phases: this is the phase problem. Chemical composition, symmetry, and additional measurements can supply constraints beyond the original pattern.^[ref]