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The experiment involving Ferenc Krausz combined a subfemtosecond soft-X-ray pulse with a few-cycle visible electric field. Its delay-dependent krypton photoelectron spectra tested the field-controlled response. The reported pulse duration was $650\pm 150$ attoseconds. Changing delay compared the emitted electron distributions at different reference phases; the spectral-width trace supplied a further duration-sensitive observable.^[ref]

The distinction from RABBITT is the measurement regime and reconstruction, rather than merely calling one trace a clock. The attosecond streaking momentum map is a limiting model; a finite-duration wave packet requires a quantum transition calculation. Inferring an emission delay also requires separating the illuminating pulse's spectral phase from the target response. The measurement supports time-dependent photoionization in a specified model, with no unique classical electron trajectory inside an atomic orbital implied.

Occupying an antibonding molecular orbital opposes a chemical bond. For equivalent $1s$ atomic orbitals of the hydrogen atom, the difference ${\sigma }_u^{\ast }={\sigma }_{-}$ vanishes on the plane halfway between the protons: every point there is equally far from both centres, so the amplitudes cancel. This nodal plane removes the contribution of this molecular orbital to electron density on that plane; it does not make an entire finite region empty. The $1s$-derived antibonding molecular orbital lies above its bonding molecular orbital partner in energy. See Field, MIT 5.61, lecture 25, pp. 1–2.

In the ${\mathrm{He}}_2$ minimal model, $({\sigma }_u^{\ast }{)}^2$ adds $N_a=2$ and cancels the bond order contribution of $({\sigma }_g{)}^2$. Opposite signs on the two lobes describe probability amplitudes, while both lobes have nonnegative probability density after squaring. The star is an orbital label, not an extra electron or an electric charge.

A plane on which an atomic orbital wavefunction vanishes. For a real p orbital oriented along $x$, it is the plane $x=0$. The probability density also vanishes on that plane.

Attosecond physics resolves changes on the scale of $10^{-18}$ seconds, especially electron dynamics. Its central trick is to convert a short optical event into an experimentally accessible energy or phase change. A broad optical spectrum provides the ingredients for a short optical pulse; their spectral phases determine when those ingredients add constructively. High harmonic generation supplies the optical spectrum, while RABBITT and attosecond streaking supply complementary timing measurements. XUV denotes extreme ultraviolet radiation.

There are two separate timing problems: characterize the incident optical pulse, then infer the response of the target. A photoelectron measurement mixes the incident spectral phase, the target's transition response and the probing electric field. Recovering one requires constraints on the others. These methods measure distributions of photoelectron energies over repeated shots, rather than photographing a moving atomic orbital.

An approximate scheme for constructing an atomic electron configuration by filling lower-energy atomic orbitals before higher-energy ones, subject to the Pauli exclusion principle. Orbital ordering can change on ionization and has exceptions in interacting chemical atoms. Selecting the free-ion ground term within a specified open-shell configuration additionally requires Hund's rules or a more detailed interaction calculation.

Occupying a bonding molecular orbital favours a chemical bond. For the two equivalent $1s$ atomic orbitals of the hydrogen atom, the sum ${\sigma }_g={\sigma }_{+}$ has constructive interference between the protons. The resulting electron density in that region helps stabilize the combined system. Its lower energy in this model follows from the Quantum Hamiltonian, not from the plus sign alone; see Field, MIT 5.61, lecture 25, pp. 1–2.

For example, $({\sigma }_g{)}^2$ in molecular hydrogen supplies $N_b=2$, hence bond order one when $N_a=0$. The sum in the molecular orbital theory toy has midpoint probability density $0.303468$, whereas the difference has zero there. The normalization factors must be included in this comparison.

A symmetry transformation acts on localized atomic orbitals both by moving their centres and by transforming their angular shapes. Only centres left in place can contribute to the trace of the corresponding group representation. At each fixed centre, sum the diagonal coefficients of the orbital transformation: a reversed p orbital contributes $-1$, whereas a fixed s orbital contributes $+1$. For Cartesian displacement vectors at a fixed atom, use the trace of the full polar-vector matrix, not merely the number of fixed components. This rule generates characters of a representation without writing its entire matrix.

For a finite group $G$ represented unitarily by $U(g)$, the central projector onto the isotypic subspace of an irreducible representation $\lambda$ is $P_{\lambda }=(d_{\lambda }/|G|){\sum }_g{\chi }_{\lambda }(g{)}^{\ast }U(g)$, where $d_{\lambda }$ is its dimension. Character orthogonality implies that the operator is identity on copies of $\lambda$ and zero on other irreducibles. For a one-dimensional irreducible, applying it to an atomic orbital gives either zero or a symmetry-adapted linear combination of that symmetry, to be normalized afterward. A multidimensional central projector selects an entire isotypic component rather than one uniquely chosen component function.

Adjacent compatible p atomic orbitals allow electron density to delocalize across more than two atoms. Resonance contributors describe aspects of this shared electronic structure.

In atomic units, the displayed integral is the direct electrostatic contribution between two normalized atomic orbitals $a,b$. It enters a two-electron energy expectation together with the exchange integral.

Crystal field theory models the effect of surrounding ligand charges or dipoles on metal atomic orbitals. Directional repulsion splits the $d$ levels. Unlike molecular orbital theory, the simplest model does not explicitly construct covalent metal–ligand bonds.

An atomic orbital with orbital angular momentum quantum number $l=2$. Five angular functions span the subshell; a ligand field can split their energies.

For two orthonormal spatial atomic orbitals, the normalized symmetric and antisymmetric two-particle factors have Coulomb energies $J_{ab}+K_{ab}$ and $J_{ab}-K_{ab}$. With common orbitals, the fermionic singlet state and triplet state therefore differ by $2K_{ab}$. This is an exchange interaction resulting from the state symmetry and the Coulomb operator, rather than a separate classical force.

A linear combination of atomic orbitals used in a localized description of directional bonding or lone pairs. Hybrid labels are models rather than directly observable fixed atomic states.

For emission take integers $n_i>n_f\ge 1$. Applying conservation of energy to the model's internal energy difference, while neglecting the much smaller whole-atom photon recoil, givesThus Johannes Robert Rydberg's Rydberg formula is a difference of two energy levels expressed as a spectroscopic wavenumber. The same constants determine every line; there is no new parameter for each electronic transition. With the chosen inputs, $R_H=1.096775834\times 10^7{\mathrm{m}}^{-1}$. All wavelengths below are calculated in vacuum, not air, and are rounded model predictions rather than historical measurements.

The conventional names commemorate Theodore Lyman and Johann Jakob Balmer. Fixing $n_f=1$ produces the ultraviolet Lyman series, beginning with the Lyman-alpha line; fixing $n_f=2$ produces the Balmer series. As $n_i\to \infty$, the wavelength approaches $n_f^2/R_H$: $91.1763\mathrm{nm}$ at the Lyman limit and $364.705\mathrm{nm}$ for the Balmer series. Crowding follows directly from $E_{n+1}-E_n\sim 2B_H/n^3$. Discreteness therefore coexists with a series limit.

Correct line positions do not give wave intensities, lifetimes or electric-dipole selection rules for hydrogen. Those require a theory of the wavefunctions and their coupling to electromagnetic radiation. The circular model also omits spin, relativistic corrections and the Lamb shift. Its successful gross energy levels do not make its assumed orbits modern atomic orbitals.

An ion is a chemical atom or a group of chemical atoms with a nonzero net electric charge. A positive ion is a cation; a negative ion is an anion. The whole entity carries the electric charge: a hydronium ion is a group of four chemical atoms with net charge $+e$. This definition agrees with ^[ref].

For an ordinary ion containing only atomic nuclei and electrons, let $N_p$ count all its protons and $N_e$ all its electrons. Each proton contributes the elementary charge $+e$, each electron contributes $-e$, and neutrons contribute zero. ThereforeThe signed integer $z$ is the net electric charge number. Removing an electron increases $z$ by one; adding an electron decreases $z$ by one. Changing the electron count leaves the atomic number, and therefore the identity of the chemical element, unchanged.

For example, a neutral sodium chemical atom has $11$ protons and $11$ electrons. Its cation ${\mathrm{Na}}^{+}$ still has $11$ protons, but only $10$ electrons, so $q=(11-10)e=+e$. A neutral chlorine chemical atom has $17$ protons and $17$ electrons; its anion ${\mathrm{Cl}}^{-}$ has $17$ protons and $18$ electrons, so $q=(17-18)e=-e$. These are particle inventories, not pictures of atomic orbitals. See 2.6 Ionic and Molecular Compounds (§2.6: ions and ionic compounds).

One sodium chloride formula unit accounts for one ${\mathrm{Na}}^{+}$ cation and one ${\mathrm{Cl}}^{-}$ anion, whose net electric charges sum to zero. Ordinary solid sodium chloride is an extended arrangement of ions, rather than discrete $\mathrm{NaCl}$ molecules. This is a useful distinction: a neutral material can contain charged constituents, and its chemical formula tells us their ratio without claiming that each pair is a separate molecule.

Ion bookkeeping connects chemistry to electric current: moving ions can transport electric charge, while stationary ions cannot supply a transport current density. In electrochemistry, both signs of ions can contribute to the same conventional current. An ion opposing a fixed electric charge is called a counterion.

The LCAO approximation builds a molecular orbital as a linear combination of single-centre atomic orbitals. For two equivalent normalized real $1s$ functions ${\varphi }_A$ and ${\varphi }_B$, choose their signs positive and define their orbital overlap $S$. At nonzero separation, $0<S<1$, and the normalized combinations areHere ${\sigma }_{+}={\sigma }_g$ and ${\sigma }_{-}={\sigma }_u^{\ast }$. Equal coefficients use the equivalence of the two centres; a general LCAO need not have equal coefficients. See Field, MIT 5.61, lecture 24, pp. 3–6: LCAO coefficients and overlap integrals.

For the Gaussian function toy's $a=1$, the two denominators are $\sqrt{2(1+S)}\approx 1.654013$ and $\sqrt{2(1-S)}\approx 1.124385$. To check wavefunction normalization, expand the square: $\int ({\varphi }_A\pm {\varphi }_B{)}^2=1+1\pm 2S$. Dividing by $2(1\pm S)$ gives one. The local probability density isThe cross term is the interference; adding the separate densities first would lose it. These formulas normalize the chosen linear combination exactly, while the restricted choice of atomic orbitals remains an approximation to an actual molecular orbital.

A metal-metal bond joins two metal centers directly through overlap of their atomic orbitals. A single bond contributes one electron to the local count at each metal in conventional electron counting. Bridging ligands can accompany direct bonding, but a short bridged separation alone does not establish its bond order.

Molecular orbital theory describes the electronic arrangement of a molecule using molecular orbitals: one-electron spatial wavefunctions extending over the combined atomic nuclei. Filling bonding molecular orbitals can stabilize a chemical bond; filling antibonding molecular orbitals opposes that stabilization. A molecular orbital is a building block of a many-electron description, rather than the entire many-electron wavefunction. See Robert W. Field, MIT 5.61, lecture 24, pp. 1–4: molecular orbitals and the LCAO approximation.

First make the interference visible with an exactly normalized one-dimensional toy. Replace the three-dimensional $1s$ atomic orbitals of the hydrogen atom by two Gaussian functions centred at $x=\pm a$, with dimensionless $x$ and $a>0$:The normalized sum and difference are ${\psi }_{\pm }=({\varphi }_A\pm {\varphi }_B)/\sqrt{2(1\pm S)}$, following the same linear combination of atomic orbitals algebra. At $a=1$, the orbital overlap is $S=e^{-1}\approx 0.367879$. At the midpoint, ${\varphi }_A(0)={\varphi }_B(0)\approx 0.455581$, givingBoth probability densities have total integral one: interference redistributes probability, rather than creating an extra electron. These are toy wavefunctions, not actual hydrogen atom orbitals or predictions of molecular hydrogen energies.

Now fill the two $1s$-derived molecular orbitals in the minimal model. The lower bonding molecular orbital is labelled ${\sigma }_g$; the upper antibonding molecular orbital is ${\sigma }_u^{\ast }$. The Pauli exclusion principle permits at most two electrons in each spatial molecular orbital, with opposite spin projections along a chosen axis. For the lowest electron configuration in this model, fill ${\sigma }_g$ first. The subscripts $g$ and $u$ denote even and odd behaviour under inversion through the midpoint; the star marks an antibonding molecular orbital. See Flowers et al., Chemistry 2e, 8.4: occupancy and bond order and Field, MIT 5.61, lecture 25, pp. 1–3: bonding, antibonding, and symmetry labels.

With $N_b$ electrons in bonding molecular orbitals and $N_a$ in antibonding molecular orbitals, the model's bond order is $b=(N_b-N_a)/2$. The three elementary counts are:

The zero bond order says this minimal model gives no net covalent bond for ${\mathrm{He}}_2$. It does not rule out every bound pair of helium chemical atoms: a very weak Van der Waals force can bind a neutral helium dimer, which has been observed experimentally. See Zeller et al., Imaging the He2 quantum halo state using a free electron laser, PNAS 113, 14651–14655 (2016), p. 14651: van der Waals binding and Luo et al., The weakest bond: Experimental observation of helium dimer, Journal of Chemical Physics 98, 3564–3567 (1993). The bond order count does not include that weak binding mechanism.

The useful surprise is that sharing alone does not determine a chemical bond: the relative quantum phase and the occupancy matter together. The same two shapes explain why adding an electron to a bonding molecular orbital increases the model's bond order, while adding one to an antibonding molecular orbital decreases it. Molecular orbital theory also accounts for the unpaired electrons and paramagnetism of molecular oxygen, which its all-paired Lewis structure misses. See Chemistry 2e, 8.4: the molecular orbital description of oxygen.

The point group of orthogonal spatial transformations that preserve a fixed molecular geometry, including the positions and chemical identities of all nuclei. Changing a conformation can change the molecular point group even when the molecular connectivity is unchanged. Its group representations on atomic orbitals depend on orbital signs and rotations as well as the permutation of centres.