For a three-light-flavor example, take up quarks, down quarks and strange quarks with the following additive quantum numbers. Here denotes electric charge in units of the positive elementary charge , is baryon number, is strangeness, is the third component of isospin, and is flavor hypercharge. An antiquark reverses all five displayed values. These are flavor coordinates, not spatial coordinates or electroweak hypercharge.
Quark flavor
Adding these columns immediately explains familiar hadrons. A proton with valence quarks has and ; a neutron with has and . A positive kaon with has , and . Thus the same constituent rules describe both baryons and mesons.
Figure 1.
Adding constituent quantum numbers distinguishes charged and neutral hadrons
. Original arithmetic examples for the three-light-flavor quark model. The lower panel contrasts two orthogonal neutral flavor combinations: identical total electric charge does not make two states identical. These are ideal flavor basis states, not a mass fit or a reconstruction of an experimental event. Details.
Two hadrons can have identical additive labels while differing in their internal state. The Lambda baryon and neutral Sigma baryon both have valence content , yet their total isospin differs. Likewise, the neutral pion flavor direction and the Eta octet state both have , but their inner product vanishes. Expanding that inner product gives . Constituent counting must therefore be supplemented by quantum superposition and the symmetry of the state.
Qubit Created 2026-09-25 Updated 2026-10-14
A qubit, or quantum bit, is a quantum system whose state space is a two-dimensional complex Hilbert space. Choose an orthonormal basis , called the computational basis. A pure state has a normalized representative , where are complex probability amplitudes and . General qubit states, including mixed states, require a density matrix. [ref].
The abstract qubit describes the chosen degree of freedom: for spin one-half, can label spin up and down along a specified axis; for photon polarization in a fixed propagation mode, they can label horizontal and vertical polarization, . These implementations share the same two-dimensional linear algebra, but their preparation and measurement in quantum mechanics use different apparatus. A qubit therefore need not be an entire two-level particle. [ref].
The usefulness of a qubit lies in controlling quantum superpositions and their relative quantum phases, then converting them into outcome probabilities with quantum gates and an appropriate measurement. One ideal computational-basis measurement returns one label, zero or one. It does not reveal both probability amplitudes, their relative quantum phase, or all the bits of a larger register's expansion. Quantum state tomography instead estimates a qubit state using many repetitions of the preparation and suitable measurement settings. [ref].
An actual preparation and measurement example is Dederick and Beck's 2014 teaching-laboratory experiment. A 405-nm laser pumped two nonlinear crystals, producing signal and idler photons near 810 nm. In their non-entangled run the source produced ; a quarter-wave plate in the signal arm changed its photon polarization to in their convention. The plate supplies a relative quantum phase between polarization components. An idler detection selected the signal trials; signal detectors measured horizontal/vertical, diagonal, and circular polarization bases on separate runs. Before the polarization analyzer, a half-wave plate at degrees selected the diagonal basis, and a quarter-wave plate at degrees selected the circular basis. Coincidence counts gave the conditional positive-outcome frequency . The reconstructed density matrix for conditioning on detector had squared quantum fidelity with and purity of a density operator : close to the intended pure state, rather than an exact ideal preparation. [ref].
Figure 1.
Ideal polarization-qubit preparation and measurements in three separate settings
. Original model schematic and exact Born-rule probabilities, not measured data or a reproduction of the experimental apparatus. The circular-basis sign uses the explicitly defined state . Details.
The model diagram explains why those settings matter. With and , the intended gives equal probabilities in both the horizontal/vertical computational basis and diagonal Hadamard basis, just as the mixed state does. In the circular basis , however, the ideal always gives the plus outcome, whereas still gives equal probabilities. These are deductions from the Born rule, not the paper's measured counts. Unequal detector efficiencies and finite samples must be accounted for when interpreting experimental frequencies; the ideal comparison assumes equally efficient detection.
Rabi cycle 2026-10-18
A Rabi oscillation is a coherent oscillation of populations in a driven two-level quantum system.
A resonant drive can transfer a quantum state from one energy eigenstate to another and then bring its population back. This is unitary time evolution: the drive exchanges energy with the selected two-level system, while total probability stays one. One complete Rabi cycle has population period ; halfway through, a Rabi pi pulse transfers the whole population in the ideal model. This makes Rabi oscillations useful for calibrating resonant quantum control, preparing quantum superpositions and supplying the pulses of Ramsey interferometry.
Ramsey interferometry 2026-10-18
Ramsey interferometry uses two coherent pulses with a free interval between them: the first creates a quantum superposition, the interval accumulates relative quantum phase, and the second converts that quantum phase into measurement probabilities. Its attraction is that an ordinary population readout can reveal the quantum coherence hidden from an energy measurement during the free interval.
Here is an ideal qubit model with an explicit pulse convention. Let , prepare , apply , evolve freely with , and apply the inverse pulse before a computational-basis measurement. The first pulse gives . Direct matrix multiplication gives
Thus the Born rule gives and . Before the second pulse, the same computational-basis measurement would give for both outcomes for every . At , the second pulse changes these probabilities to and . If the two pulses have the same sign instead, the output labels interchange: the pulse convention is part of the prediction.
Figure 1.
An ideal Ramsey sequence turns relative phase into population
. Original pulse-sequence schematic and exact probabilities for . Dashed lines show a separate readout with the second pulse omitted. Instantaneous perfect pulses and noiseless free evolution are idealizations, not experimental measurements. Details.
In a pulse experiment the phase is measured relative to the oscillator supplying the coherent pulses. In a rotating frame, write the free Hamiltonian operator as with signed angular frequency difference in the chosen labeling convention. A free interval then accumulates ; changing the second pulse's phase changes the analysis direction. This comparison makes Ramsey interferometry useful for measuring frequency differences and diagnosing loss of quantum coherence.
For example, suppose the first pulse has prepared a density matrix with equal populations and transverse Bloch vector length :
The same inverse analysis pulse yields . The pure state case gives the full ideal fringe; the mixed state gives the flat result . This is a controlled mathematical comparison, not a fit to an experiment. Experimental contrast alone does not identify quantum decoherence: imperfect preparation, pulse errors and readout errors can also reduce it.
Schrödinger equation Created 2026-09-24 Updated 2026-10-20
The Schrödinger equation governs the evolution of a quantum state between instances of measurement in quantum mechanics. For a particle of mass moving in a prescribed real potential energy , its position wavefunction satisfies
Here is the Planck constant, is the Laplace operator, and the Hamiltonian operator combines kinetic energy with potential energy. Specify an initial wavefunction, an operator domain and any boundary conditions: the differential expression alone does not completely specify a physical model. The Born rule then turns the evolving probability amplitude into position probabilities through and integration over a region.
This scalar Schrödinger operator describes nonrelativistic quantum mechanics, with relevant momenta much smaller than , where is the speed of light. It omits the constant rest energy , assumes fixed particle number, and suppresses active spin dynamics and coupling to a magnetic vector potential. A free electron with a fixed, uncoupled spin state can still use this scalar model; the Pauli equation supplies the additional spin components and magnetic coupling when needed. A prescribed real describes a closed evolution model or an approximation in which the source of that potential energy is treated as external. Dissipation, particle creation and a general measurement in quantum mechanics need further modelling.
For a time-independent self-adjoint Hamiltonian operator, the spectral theorem defines unitary time evolution by
Initial states in the operator domain satisfy the differential equation in the Hilbert space sense; the unitary operator also evolves all other states in that Hilbert space. Time-dependent Hamiltonian operators need suitable regularity and domain hypotheses; their evolution is not generally the exponential of .
The local reason for conservation is especially tangible. Multiply the Schrödinger equation by the complex conjugate , subtract its conjugate multiplied by , and use the fact that the real potential energy terms cancel. For smooth wavefunctions this gives the probability continuity equation
The divergence theorem identifies the change in probability inside a region with minus the outward probability current. Decay at infinity, or appropriate probability-conserving boundary conditions, preserves wavefunction normalization. Conservation of total probability does not require a stationary probability density.
Its usefulness comes from being a linear partial differential equation: quantum superpositions of solutions are solutions, while different quantum phases can produce interference. For a fixed Hamiltonian operator, the time-independent Schrödinger equation finds the energy eigenstates; each then acquires just its own time-dependent quantum phase. One eigenvalue problem therefore organizes both allowed energies and the evolution of arbitrary quantum superpositions, with a continuous spectrum included when required. This is the attractive bridge between a spatial wave problem and a clock: energy differences determine the rate at which relative quantum phases change. It makes atomic spectral lines, quantum tunnelling and quantum scattering calculable from a specified model.
For an explicit example without confinement, take a free particle on the whole line, , initially in a Gaussian wave packet with position standard deviation and mean momentum :
Unlike a single plane wave, this wavefunction satisfies wavefunction normalization. A Fourier transform writes it as a quantum superposition of plane waves. Their dispersion relation is , so each Fourier component gains the factor . Completing the square in the resulting Gaussian integral gives
with the square root chosen continuously from . Its position probability density and standard deviation are
The centre moves with the group velocity and the wave packet spreads because different wavenumbers have different group velocities. This is unitary wave dispersion, without a random force or loss of probability. Independently, the initial momentum standard deviation is and the initial position-momentum covariance vanishes. Free evolution gives in the Heisenberg picture, hence
This independently checks the spreading law. The Gaussian integral of is one at every time; the decreasing peak is exactly offset by increasing width.
As hypothetical preparation parameters, choose a free electron with and . Using and gives
The rounded electron mass uses the 2022 adjustment.[ref] At , the centre is and ; at , they are and . The mean kinetic energy stays
It includes both mean motion and the momentum spread. The mean speed is about and the momentum spread corresponds to , making the nonrelativistic model accurate for the appreciably occupied part of this ideal Gaussian distribution. Its mathematically unbounded tails are an idealization.
Figure 1. . Calculated electron position probability densities for the hypothetical preparation above, together with the position standard deviation. The area under every curve is one. The dashed width curve illustrates pure translation without spreading for comparison; it is not the free solution. No curve represents measured data. Source. Details.
The complex width also explains where the probability goes. Write , where is the dimensionless quantum phase. Differentiating the exact solution gives
Relative to the moving centre, the probability current points outward on both sides for . This is a flux statement, not an additional assumption about individual particle trajectories. At and , the relative flow speeds are , about . The probability within a moving interval of half-width falls from about initially to at , exactly because of this outward probability current.
Figure 2.
Curved quantum phase drives spreading probability current
. The same free Gaussian wave packet at . With , removing the carrier and a spatially constant quantum phase leaves . The right panel plots : negative to the left, positive to the right. Flux through the marked moving interval endpoints explains its decreasing probability. Source. Details.
Historically, the 1926 Quantisierung als Eigenwertproblem (Erste Mitteilung) by Erwin Schrödinger began with the stationary hydrogen atom problem. It distinguishes discrete negative energies from a positive continuous spectrum; it is not yet the general evolution equation displayed above.[ref] The opening of quantum mechanics discusses its original vibrating-string analogy.
In the 12 December 1933 lecture The fundamental idea of wave mechanics by Erwin Schrödinger, Erwin Schrödinger explains the move from independent rays to waves through diffraction, then applies that analogy to atomic physics. His closing pages explicitly acknowledge the difficulty of reconciling wave language with observed particle tracks. This retrospective physical argument motivates the model; it does not derive the modern Born rule from classical mechanics.[ref]
The dates separate proposal from measurement: the de Broglie wavelength belongs to the 1924 thesis, the Schrödinger equation to 1926, and the Davisson–Germer experiment's electron diffraction beams to 1927.[ref] That linked experiment describes the prepared nickel crystal, evacuated electron gun, angular collector scans, retarding-potential selection and heating controls. Its measured collector electric current tests wave-dependent scattering probabilities; it neither measures a wavefunction directly nor establishes this equation uniquely.
Consider an original balanced-readout model, rather than a fit to the experiment. Let , with a normalized prior probability and . A detected chemical atom has outcome . Define the conditional probabilities
Here is the accumulated quantum phase per photon, the controlled analysis quantum phase, and the fringe contrast. The two probabilities sum to one for every . Actual calibration may also require an offset and asymmetric detection errors; alone does not specify a quantum instrument.
Assume no photon number change during the record and fresh independently prepared atomic meters. For observed outcomes at recorded settings , the Born rule and Bayes' theorem give
The posterior probability is defined only for . Summing its numerator over proves normalization. This is also the update of diagonal elements of a field density operator under a measurement in quantum mechanics; it does not assume that an initial quantum superposition was an unknown pre-existing integer. The observed settings are part of the record, especially when selected adaptively.
For an exact finite example take , , and . An outcome at has likelihood , giving . Another at gives . A subsequent at gives
Thus three atomic records raise the posterior probability of from to , while leaving finite uncertainty. No one of these outcomes identifies with certainty.
Figure 1.
Synthetic atomic records progressively concentrate a photon-number posterior
. Original simulation, not laboratory data: , uniform prior, , , four cyclic analysis phases, and a fixed simulated . Cavity loss is omitted. Individual updates can broaden the distribution even though this record eventually concentrates. Details.
The periodic likelihood function imposes an identifiability limit. If for an integer , then for every setting: the posterior odds between and never change. Varying can resolve a cosine reflection ambiguity within a period, but cannot remove this exact period. Changing can supply additional information. A finite cutoff is therefore a physical assumption to justify, not evidence that excluded high photon numbers were absent. At no outcome changes the prior probability; at neither binary outcome has an exactly zero likelihood.
The no-loss assumption also has a time limit. In an original zero-temperature loss model, let . A Fock state loses its first photon at rate , so its survival probability is and its mean lifetime is for . Several records must be acquired within that lifetime to identify a plateau. When losses matter, first predict using a normalized transition matrix, then apply the atomic Bayesian inference update to . Thermal excitation requires upward transitions too. A delayed or broadened inference after a jump need not indicate that an atom caused the jump.
Single-photon state 2026-10-24
A single-photon state lies in the one-excitation sector of the quantized electromagnetic field. It can be a quantum superposition over spatial ports or temporal modes while its total photon number remains one. Squared coefficients give exclusive event probabilities only when the corresponding wavepacket modes are orthonormal; overlapping temporal histories must be added coherently.
Slater determinant 2026-10-14
A Slater determinant extends two-particle antisymmetrization to fermions. Here contains position and spin or other internal variables. Distinct orthonormal one-particle states give the normalized wavefunction displayed in the title. Repeating a one-particle state repeats a column of the determinant, so the wavefunction vanishes. Exchanging particle slots exchanges rows and reverses its sign. A general fermionic quantum state can be a quantum superposition of Slater determinants; it need not be one Slater determinant.
Measure the commuting stabilizer generators and in that order. Use error syndrome bit for eigenvalue and bit for eigenvalue . For the Pauli X gate on physical qubit , every row holds for arbitrary normalized . This ordered parity-check convention follows [ref]:
ErrorState before recovery eigenvaluesError syndromeRecovery
Each pair of computational basis words within a row has the same two parities. Consequently the projective measurement reveals the row without distinguishing its two amplitudes. For example, becomes under . Both checks give with probability one, and applying restores both coefficients exactly, including the relative phase .
One implementation uses two quantum ancillas initialized to . Two controlled-NOT gates from data qubits 1 and 2 to the first quantum ancilla write their parity; two more from data qubits 2 and 3 to the second quantum ancilla write the other parity. Measuring only the quantum ancillas in the computational basis gives . Measuring the individual data qubits instead would reveal the encoded computational basis value and destroy the unknown quantum superposition. The existing coherent syndrome extraction for the three-qubit repetition code uses the alternative ordered checks , so its bit labels differ from this table.
Figure 1.
Parity checks identify a bit flip without reading the logical amplitudes
. Details.
The recovery also handles coherent errors. Put . Their images of the code are mutually orthogonal, giving , the Knill--Laflamme condition for this family. For any linear combination , its component in sector is . Measuring that error syndrome has probability on the normalized erroneous state, and recovery returns . More generally one recovery quantum channel corrects every noise quantum channel whose Kraus operators belong to this span. The assumption concerns the whole jointly correctable family; it does not extend to the span of arbitrary single-site Pauli errors. [ref].
A fully computed coherent example is the unitary operator . At it gives
The error syndromes and occur with probabilities and , independently of . Doing nothing for and applying for restores the same logical qubit in both branches; the scalar in the second branch is an irrelevant global phase. This is an example of linearity of coherent quantum error correction, rather than an assumption that the original error was a classical random bit flip.
Time-independent Schrödinger equation Created 2026-09-24 Updated 2026-10-20
For a time-independent Hamiltonian operator , an energy eigenstate satisfies
For a one-dimensional particle of mass in a real potential energy ,
Its full time-dependent wavefunction is : substitution in the Schrödinger equation checks both the minus sign and the factor . Thus an energy eigenstate has stationary position probability density, even though its quantum phase evolves. The boundary conditions and operator domain are part of this eigenvalue problem, selecting physically allowed solutions; the infinite square well and Radial Schrodinger equation for the hydrogen atom give complementary confined examples.
For a complete discrete orthonormal basis of energy eigenstates, linearity gives , with . Cross terms in oscillate at angular frequencies . A continuous spectrum requires the corresponding spectral integrals; for a free particle on the whole line, individual plane waves are generalized eigenfunctions, and a normalized Gaussian wave packet is their integral quantum superposition. Adding a spatially constant real to shifts every energy eigenvalue by and multiplies the full state by , a global phase; energy differences, position probabilities and probability current are unchanged.
Trapped-ion quantum control Created 2026-10-18 Updated 2026-10-24
Trapped-ion quantum control prepares an ion's internal quantum state, couples it to quantized motion with laser pulses, and measures the result through state-dependent fluorescence. Its appeal is access to both a controllable two-level system and a quantum harmonic oscillator in one apparatus.
Confinement, preparation, control and readout solve different problems. The Paul trap's RF electric field confines the ion through its RF-averaged trapping potential; it still produces Paul trap micromotion. Doppler cooling and resolved sideband cooling reduce motional excitation. Optical pumping selects an internal quantum state. A coherent pulse then changes amplitudes, while electron shelving converts an internal population into a detectable stream of photons. A bright/dark count by itself does not reveal a quantum superposition's relative phase; an additional controlled rotation before detection can make that phase affect the measured population.
Figure 1.
Trapped-ion preparation, coherent control and fluorescence readout
. Original functional diagram. The level roles illustrate mercury-ion electron shelving; the later beryllium Raman experiment uses hyperfine states instead. Geometry and energy gaps are schematic. Cooling, coherent interrogation and detection are distinct stages. Details.
Consider one chosen model at a fixed total energy, with two open scattering channels, no absorption and no omitted outgoing modes. Channel 1 leaves the target unchanged; channel 2 excites it. Let and . For the same projectile mass, conservation of energy then requires a target excitation . These are hypothetical parameters, not a fit to a particular atom. Each incoming or outgoing mode is normalized to unit probability current; the outgoing modes will have the angular profiles specified below.
Choose the S-matrix
This phenomenological unitary matrix specifies the channel conversion; it is not derived here from an interaction potential energy. For incidence in channel 1, its first column gives the outgoing flux amplitudes
To recover ordinary wave coefficients relative to an incident coefficient one, undo the velocity normalization:
Thus is allowed: channel 2 travels more slowly. Its outgoing probability current fraction is , not . Renormalizing the unweighted squares would give and , the wrong probabilities. More generally the ordinary coefficient map is , with ; it obeys . The conserved quantity is the squared coefficient norm weighted by velocity, which represents probability current.
Now specify an original angular realization of these two outgoing modes, with scattering angle and no azimuth dependence:
The first normalization follows from , where . These angular profiles define the modes of this model; they are not asserted to follow from Born's approximation or an atomic potential energy. The joint directional probability densities are
Figure 1.
Complex angular amplitudes become channel-resolved scattering intensity
. Original two-channel model. Left: arrows in the complex plane show , the angular factor of . Right: the joint directional probability densities , per solid angle, retain the channel flux weights and . The shaded interval is the cone ; its probability requires the measure , not the area under a curve against degrees. These are chosen amplitudes, not historical measurements. Source. Details.
Suppose a detector accepts the cone , with full azimuth and unit efficiency. Its angular fractions within the channels are
Multiplying the angular fractions by the outgoing flux weights gives
For independent incident events, the expected values are therefore and accepted detections, compared with and over all directions. The remaining expected events fall outside the cone. The chosen incident number makes the expectations integers; actual counts fluctuate. Conditional on a detection inside the cone, the channel probabilities are and , rather than and . Angular acceptance changes the observed channel proportions even with equal detector efficiencies.
Figure 2.
Velocity weighting and angular acceptance determine expected channel counts
. Original model with incident events. Left: raw squared wave coefficients and become conserved outgoing flux fractions and after multiplying by . Right: all-direction expectations and become and inside the cone. Bars show calculated expected values, not a generated sample or experimental counts. Source. Details.
The final atomic states are orthogonal, so ignoring the atomic readout adds the two channel intensities; it does not produce . Coherent paths that reach the same final state can instead interfere, as the existing probability amplitude and quantum superposition examples demonstrate. The distinction is physical distinguishability of final states, not whether the detector operator chooses to display their labels. Flux normalization and angular integration make the scattering interpretation useful: they turn complex outgoing waves into conserved event weights and then into the statistics of a specified detector.
For a deliberately simplified neutrino oscillation calculation, take two neutrino flavors related to two mass eigenstates by a real rotation matrix with angle . A quantum superposition acquires different phases during propagation; projecting back onto the initial neutrino flavor gives the probability
Here is path length and is neutrino energy; the numerical coefficient incorporates unit conversion.
The paper states the corresponding conversion formula.[ref]
The path dependence has a geometrical origin. In an original spherical-Earth model, let be the radius and a fixed production height, neglecting detector depth. Let be the zenith distance of the direction in the sky from which the neutrino arrives, so means downward propagation. The backward ray from detector to production obeys . Its positive solution is
Thus and . The calculation explains why opposite directions test very different baselines, rather than attributing every observed direction to the same travel distance. Actual production heights and the angle between the outgoing charged lepton and incoming neutrino smear that relationship.
For an original chosen example, set and . At , gives , while gives . The first minimum is at . These are stipulated inputs, not a fit to the 1998 data. A broad distribution of true , together with energy and directional uncertainty, smooths the sharp minima.
A direct amplitude check makes the mechanism explicit. Define
Then . Taking its squared absolute value yields the displayed survival formula because . Unitarity gives : disappearance from one channel becomes conversion to the other within this closed model.
This illustration does not describe all solar neutrino propagation. Coherent forward scattering in matter changes the effective propagation operator, and three active neutrino flavors require a larger mixing description. Even in the simplified model, neutrino oscillation measures a squared-mass difference; it does not determine the absolute neutrino mass.
Wave function Created 2026-10-13 Updated 2026-10-20
A wavefunction is the position representation of a pure state. In the one-dimensional model used here, takes values in the complex numbers, and the Born rule gives
The probability density has units of inverse length; the wavefunction has units of inverse square root of length. A value of at a point is not itself a probability: probabilities come from an integral over a region. For the infinite square well ground state, , whereas the probability of the exact single point is zero. The interesting question is how much probability a finite interval contains.
Two wavefunctions differing only by a global phase represent the same pure state. Relative quantum phases between components of a quantum superposition affect matter-wave interference, so retaining the full complex number amplitude is essential. This scalar description covers a particle without active spin degrees of freedom; a general electron wavefunction can have two spin components, with the position probability density obtained by adding the squared modulus of each component.
Wavefunction normalization Created 2026-10-06 Updated 2026-10-20
Wavefunction normalization makes the total Born rule probability equal to one. In an orthonormal basis of energy eigenstates, is normalized precisely when .
For a proposed infinite square well mode , the integral of its squared modulus is . Thus wavefunction normalization requires ; choosing real and positive fixes a convenient global phase. For the equal quantum superposition , orthogonality makes the integrated cross term zero, leaving . The cross term can nevertheless be nonzero locally: normalization constrains total probability, not the shape of its probability density.
Zero-temperature filling of finite fermion levels Created 2026-10-14 Updated 2026-10-20
For complete energy eigenstates of a one-particle Quantum Hamiltonian for identical noninteracting fermions, order their energies . At fixed particle number , the Quantum Hamiltonian and the particle-number constraint are
The ground state occupies the lowest complete one-particle states. A short minimization argument suffices: moving an occupant from a higher energy to an empty lower energy decreases the total energy. This filling describes the ground state at temperature ; exclusion by itself also applies to excited quantum states and at positive temperature. The underlying thermal description is the Fermi-Dirac distribution.[ref]
If the last occupied energy belongs to a group of one-particle states at the same energy and of them must be occupied, with all lower states filled, the ground state subspace has dimension . Exclusion does not select a particular basis or a particular quantum superposition in that subspace. The factor of two for an electron spatial orbital assumes both spin projections are included; a model restricted to one spin projection has only one state per spatial orbital. A magnetic field can split the degenerate energy levels, and interactions can change the lowest-energy electron configuration. Thus this finite noninteracting filling rule is not a complete prescription for interacting chemical atoms.