Excited state Created 2026-09-24 Updated 2026-10-14
In the stationary-state terminology used here, an excited state is a normalized energy eigenstate with energy eigenvalue , where is an attained ground-state energy. Its excitation cost above the ground state is . Several energy eigenstates can share one excited energy eigenvalue through degenerate energy levels. An arbitrary quantum superposition with energy expectation value above need not be a single stationary excited state; its energy content is described by its Born rule probabilities or, for a continuum, its scalar spectral measure.
An excited state can be a stationary state: the second infinite square well mode is an immediate example. Spontaneous photon emission is a transition caused by coupling matter to the electromagnetic field; it is absent from an isolated matter-only Hamiltonian operator. The relevant energy eigenstate of that isolated model is therefore not automatically an energy eigenstate of the full interacting system. This distinction explains how an ideal stationary excited state can approximate a state with a finite experimental lifetime. See electric-dipole interaction for the coupling used in the simplest optical model.
For a one-photon transition between stationary internal states, neglecting recoil, conservation of energy requiresHere is the Planck constant and is the photon frequency. Energy matching alone does not guarantee a transition: in the electric-dipole interaction approximation its strength also involves the matrix element , where is the electric dipole moment operator and specifies photon polarization. A zero matrix element gives an electric-dipole selection rule. Thus an absent optical line does not prove the corresponding energy eigenvalue is absent; a different interaction can couple different states. [ref]
https://farside.ph.utexas.edu/teaching/qmech/lectures/node121.html. Richard Fitzpatrick, Quantum Mechanics, Selection Rules
. The Franck-Hertz experiment gives a particularly instructive comparison between collision excitation and photon emission.The first excited state terminology assumes a least energy eigenvalue above . Such a next level is not guaranteed by quantum mechanics: a continuous spectrum can start immediately above the spectral bottom, or energy eigenvalues can accumulate there. For example, a Hamiltonian operator with energy eigenvalues , where , has a ground-state energy zero but no least positive energy eigenvalue: every candidate is exceeded downward by . A free particle on the whole line has neither a ground state nor a first stationary excited state. Each use of a discrete excitation ladder therefore needs a specified Hamiltonian operator and its boundary conditions.
Freedman-Clauser experiment Created 2026-10-18 Updated 2026-10-20
In 1972, Stuart J. Freedman and John F. Clauser excited a calcium beam from an oven with a filtered deuterium arc lamp. A calcium emission cascade supplied paired photons; an optical lens system, optical filters, removable glass-plate polarizers and cooled photomultipliers selected their linear polarizations. They compared coincidence circuit rates at relative angles and , normalized with polarizers removed. Alternating configurations controlled drift; delayed counts estimated accidental coincidences. The violation agreed with quantum mechanics, conditional on their explicit assumption that passage through a polarizer did not change a photon's detection probability. This was a static-analyzer test with a detection loophole, rather than the ideal four-output CHSH inequality statistic.[ref]
George Wheland 2026-10-20
Harish-Chandra 2026-10-31
High harmonic generation Created 2026-10-18 Updated 2026-10-20
High harmonic generation converts an intense driving electric field into radiation at high integer multiples of its frequency. High harmonic generation in a gas is a process in nonlinear optics: an electron can leave a neutral target by tunnel ionization, gain kinetic energy in the driving electric field, and return to radiate upon recombination. This three-step picture is an approximate account of a probability amplitude for emission in quantum mechanics, not a measured path of one electron.[ref]
Generation and Measurement of Isolated Attosecond Light Pulses by Michael Hentschel. Generation and Measurement of Isolated Attosecond Light Pulses, slide 5: tunnelling, acceleration and return
Why odd multiples? In an ideal centrosymmetric gas driven by a single frequency, assume the radiating electric dipole moment satisfies , where is the driving period. Its Fourier series coefficient obeys , so every even coefficient vanishes. A finite envelope, an oriented target or an additional driving frequency can invalidate that symmetry argument. Producing many odd components also does not prove that their spectral phases form a short optical pulse.
The 1988 report involving Anne L'Huillier observed odd multiples of a driving wavelength in rare gases, reaching order 33 in argon. The unexpectedly slow fall of yield beyond the fifth order supplied a broad spectral plateau. A spectral observation alone did not establish the relative spectral phases needed for an attosecond pulse train.[ref]
Multiple-harmonic conversion of 1064 nm radiation in rare gases by M. Ferray and others. Multiple-harmonic conversion of 1064 nm radiation in rare gases, abstract
Hydrogen atom Created 2026-09-24 Updated 2026-09-24
Ion pair 2026-10-13
An ion pair is an associated cation and anion. An isolated ion pair lacks the extended neighbourhood of an ionic crystal. In a chemical solution, ion pairs can coexist with more widely separated ions; their abundance depends on conditions. A neutral gas-phase sodium chloride molecule can be treated as a discrete entity, with its own quantum mechanics and dissociation products. That use of molecule does not describe the constituents of ordinary solid sodium chloride.[ref]
The Feynman Lectures on Physics, Volume II by Richard Feynman and others. §8–3, distinction between vaporized NaCl pairs and separated gaseous ions
[ref] John Clarke (physicist) Created 2026-10-24 Updated 2026-10-31
A physicist researching superconducting quantum interference devices and quantum-limited measurements.[ref]
John Clarke | Physics by University of California, Berkeley, Department of Physics. Research Interests: superconducting quantum-interference devices and quantum-limited measurements
Portrait of John Clarke (physicist)
. UC Berkeley. CC BY 4.0, via Wikimedia Commons. Source. John Clauser Created 2026-10-24 Updated 2026-10-31
A physicist who performed experimental tests of Bell inequalities.[ref]
Professional profile of John Francis Clauser (johnclauser.com). Self-authored opening identity paragraph.
Portrait of John Clauser
. Peter Lyons, photograph; Adem, existing portrait crop. CC BY-SA 4.0, via Wikimedia Commons. Source. John M. Martinis Created 2026-10-18 Updated 2026-10-31
A physicist researching superconducting devices and quantum computers based on Josephson junctions.[ref]
John Martinis by University of California, Santa Barbara. Distinguished Professor; research paragraph on superconducting devices and Josephson-junction quantum bits
Portrait of John M. Martinis
. David Orban, Flickr photograph, 13 February 2007; existing Commons crop. Creative Commons Attribution 2.0 Generic., via Wikimedia Commons. Source. John Stewart Bell Created 2026-10-24 Updated 2026-10-31
Author of the 1964 Bell theorem argument.
Portrait of John Stewart Bell
. CERN, portrait of John Bell, June 1982; CERN archive record 1823937. CC BY 4.0, via Wikimedia Commons. Source. Kronig-Penney model Created 2026-09-24 Updated 2026-10-14
The delta-comb Kronig-Penney potential is
Kurt Gottfried Created 2026-10-18 Updated 2026-10-24
Lewis structure Created 2026-10-13 Updated 2026-10-31
Before calculating electronic energy, ask a simpler question: where can the available valence electrons go? A Lewis structure makes that budget visible, and nitrate shows why a correct budget can still require several resonance structures.
A Lewis structure records which chemical atoms are connected in a molecule or ion and how its valence electrons are allocated. One line represents one bond pair, two lines two bond pairs, and three lines three bond pairs; two dots beside a chemical atom represent one lone pair. The marks are a counting language, rather than measured electron positions. See the IUPAC Gold Book, Lewis formula.
For water, , the budget is valence electrons. Two O–H lines use four electrons; the other four form two lone pairs on oxygen. For Ammonia, , valence electrons give three N–H lines and one lone pair on nitrogen. Both molecules contain four electron pairs, but their allocations differ. Each shared bond pair is counted once in the total budget, even though both endpoints count it when checking the octet rule.
Eight valence electrons in each molecule: water has two bond pairs and two lone pairs; Ammonia has three bond pairs and one lone pair
. Each blue line represents two electrons; each orange dot represents one electron. The oxygen and nitrogen each count eight electrons locally, while each hydrogen counts two. These are schematic Lewis structures, not predictions of molecular shape or electron trajectories. Details.A practical construction method is:
- Add the neutral chemical atoms' valence electron counts. Add one electron for each unit of negative electric charge, or subtract one for each unit of positive electric charge.
- Choose candidate connections and put one bond pair on each. Hydrogen normally has one connection in these simple Lewis structures.
- Place remaining electrons as lone pairs, checking the octet rule. If an endpoint has eight electrons but the central chemical atom lacks them, try converting an endpoint lone pair into an additional bond pair, keeping the total budget fixed.
- Compute every formal charge and check its sum against the net electric charge. Compare reasonable candidates, including chemical resonance when several allocations share the same connections.
For carbon dioxide, valence electrons. Starting with two single C–O connections leaves twelve electrons, enough for three lone pairs on each oxygen, but only four electrons around carbon. Converting one lone pair from each oxygen into a second bond pair gives . Eight electrons are in the four bond pairs, and eight are in four lone pairs, two on each oxygen. Carbon has no lone pair; all three chemical atoms satisfy the octet rule, and all three formal charges vanish.
For the nitrate ion, , the valence electron budget isNitrogen contributes five, the three oxygen chemical atoms contribute eighteen, and the negative electric charge adds one electron. Start with nitrogen connected to each oxygen by one bond pair: those three lines use six electrons. Put the remaining eighteen electrons into three lone pairs on each oxygen. Each oxygen now satisfies the octet rule, but nitrogen counts only six electrons. Reassign one oxygen lone pair as a second bond pair on its N–O connection. This changes the allocation without adding an electron; it applies the construction procedure in Flowers et al., Chemistry 2e, 7.3: drawing Lewis structures.
The resulting nitrate Lewis structure has one N=O connection and two N–O connections. Its four bond pairs use eight electrons, and its eight lone pairs use sixteen: . The doubly connected oxygen has two lone pairs; each singly connected oxygen has three; nitrogen has none. All four chemical atoms satisfy the octet rule. Any of the three oxygen chemical atoms can supply the additional bond pair, giving the three equivalent resonance structures below.
Why not draw three N=O connections to make the ion look symmetric? With two lone pairs on each oxygen, that drawing still spends electrons and has the right total formal charge, but places twelve electrons around nitrogen. It fails the octet rule for this second-period chemical element. Three equivalent resonance structures express the symmetry without that invalid local count.
The economy is beautiful: a handful of dots and lines rules out many impossible counts and identifies lone pairs that can participate in acid-base chemistry. A Lewis structure helps choose rational candidate connections before a detailed quantum chemistry calculation. It does not specify a complete many-electron wavefunction, actual electron density, or molecular geometry. Adding the separate VSEPR model, described in Chemistry 2e, 7.6: molecular structure and polarity, predicts bent water and pyramidal Ammonia; the layouts above alone make no such prediction. Molecular orbital theory supplies a richer electronic description, including the unpaired electrons of molecular oxygen that an all-paired Lewis structure misses.
In 1916 Gilbert N. Lewis proposed two-dot notation for the shared electrons of a chemical bond and fuller dot formulae for the outer electrons, explicitly relating a shared pair to the existing single-line notation. See Lewis, The Atom and the Molecule, JACS 38, 762–785 (1916), pp. 777–778, available as an [ref]
https://zenodo.org/records/1429068. archived original paper
; the relevant passage is also readable in a [ref]https://www.chemteam.info/Chem-History/Lewis-1916/Lewis-1916.html. transcription of the original paper
. The modern quantum mechanics interpretation should be distinguished from his historical model of fixed outer electrons. Lucien Hardy Created 2026-10-20 Updated 2026-10-31
Lucien Hardy; portrait hosted by Perimeter Institute
. Magnetic pseudomomentum 2026-10-31
For a charged particle in a uniform magnetic field, the symmetric gauge makes the displayed magnetic pseudomomentum a conserved quantity when no other position-dependent potential breaks translation symmetry. It differs from the kinetic momentum . With , Hamilton's equations for give and , proving conservation of and . The charge factor is necessary unless it has already been absorbed into the field convention. In quantum mechanics the transverse components need not commute, even though each commutes with this Hamiltonian operator; magnetic translation algebra records that distinction.
Masaki Oshikawa Created 2026-10-20 Updated 2026-10-31
Portrait of Masaki Oshikawa
. External portrait hosted by Institute for Solid State Physics, University of Tokyo. Source. Mathematical physics Created 2026-09-24 Updated 2026-10-05
Matrix element Created 2026-09-24 Updated 2026-10-18
For a linear operator on an inner product space with an orthonormal basis , its matrix elements are , using the convention that the inner product is linear in its second argument. For a finite-dimensional space, the expansion explains why these numbers represent the linear operator in that basis. In quantum mechanics, the expression is also called a matrix element between the two states; it need not be diagonal or an expectation value.
Mechanics 2026-10-24
Study of physical motion, interactions and their dynamical laws. Classical mechanics and quantum mechanics give different descriptions within this broad subject.
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