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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.

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.

In the orthogonal nearest-neighbour tight-binding model,The on-site integral ${\alpha }_s$ sets the band centre, while the hopping integral ${\beta }_s$ describes coupling between neighbouring orbitals. With a consistent phase convention, the bonding combination at the zone centre has ${\beta }_s<0$.

For p orbitals directed along the chain, useHere every positive $p$ lobe points in the same spatial direction. Neighbouring equal-sign coefficients then bring opposite-sign facing lobes together and make the zone-centre combination antibonding; the alternating zone-boundary combination is bonding. Thus the usual axial $p$ hopping has the opposite sign to $s$ hopping. Orbital phase and the sign of one-dimensional hopping must be treated consistently; replacing only ${\alpha }_s$ by ${\alpha }_p$ while silently keeping the same physical hopping sign would give the wrong band ordering.

The opposite spatial parity of the s orbital and axial p orbital gives opposite signs for left and right $s$–$p$ hopping. With real ${\beta }_{sp}$, one consistent Bloch-basis convention givesThe resulting energies areThus s-p mixing in a one-dimensional tight-binding chain lowers the lower branch and raises the upper branch wherever the coupling is nonzero. For separated atomic levels, the lower branch remains mainly $s$ and the upper mainly $p$, with increasing admixture where their uncoupled energies approach.

The upper-right panel of the figure in part (a)(ii) compares the mixed curves with dashed unmixed curves. The mixing vanishes at both $k=0$ and $\pi /a$, so those endpoints remain unchanged. If the unmixed curves approach or cross in the interior, the nonzero coupling produces an avoided crossing.

Denote the two complex spatial atomic orbitals by ${\psi }_{+}$ and ${\psi }_{-}$, retaining the same spin state. With the phases specified by the supplied spherical harmonics, chooseThe two original atomic orbitals are orthonormal, so the squared coefficients add to one and these combinations are normalized and mutually orthogonal. Explicitly,which are real spatial wavefunctions. An overall sign on either orbital has no physical consequence.

These are the familiar $2p_x$ and $2p_y$ p orbitals. Each has two lobes of opposite wavefunction sign, with an atomic-orbital nodal plane through the atomic nucleus: $x=0$ for $2p_x$ and $y=0$ for $2p_y$. The sign is a phase convention, not a positive or negative electric charge; the probability density is nonnegative on both lobes.

An internally consistent elementary orbital hybridisation model is $s{p}^2$ at carbon and $sp$ at both nitrogen atoms; the hydrogens use $1s$ orbitals. The three carbon hybrids form two C–H sigma bonds and one C–N sigma bond, leaving one perpendicular p orbital. The central nitrogen uses opposite $sp$ hybrids for its two collinear sigma connections, leaving two perpendicular p orbitals for the two pi systems.

At terminal nitrogen, one $sp$ hybrid points toward the central nitrogen and the other houses an axial lone pair. One perpendicular p orbital forms the second, N–N-only pi system; the other participates in the three-atom C–N–N pi system. This description remains the same across both resonance contributors; counting lone-pair domains in just one drawing and assigning a different terminal hybridisation to each contributor would obscure the delocalization. orbital hybridisation is a useful choice of localized basis, not a uniquely measurable label: advanced treatments of diazomethane require a superposition of bonding patterns.^[ref]

carbon uses strong 2s/2p-derived covalent bonding, whereas retention or involvement of the low-energy Pb 6s pair distinguishes the two lead oxides. In CO, carbon has an approximately triple-bonded description with one carbon lone pair; the latter has substantial 2s character, while the sigma and two pi bonding combinations involve the valence shell, particularly carbon 2p orbitals for the pi bonds. In CO${}_2$, carbon is formally in oxidation state +4 and its four valence electrons participate in two strongly covalent C=O double-bond frameworks. A localized account uses sp hybrids for sigma bonding and two p orbitals for the pi systems. oxidation states are bookkeeping devices here: neither molecule contains a bare C${}^{2+}$ or C${}^{4+}$ ion.

In PbO, the Pb(II) description removes or employs mainly the two 6p electrons, retaining a relatively low-energy 6s${}^2$ pair. In PbO${}_2$, the Pb(IV) description additionally involves those two 6s electrons. The stabilization and poor availability of that pair underlie the inert-pair effect and the relative preference for Pb(II) chemistry. “Inert” does not mean that the 6s electrons have zero influence on bonding or shape: mixing with oxygen states and empty Pb states can make the Pb(II) lone pair stereochemically active. The more ionic formal electron counts in the lead oxides and the covalent molecular-orbital description of the carbon oxides are complementary models, not literal assignments of individual electrons to immutable atomic orbitals.^[ref]

Strong ligand-to-metal pi donation is favoured by an occupied ligand p orbital and a suitable empty metal d orbital of matching symmetry, with reasonably similar energies and good spatial overlap. Small donor atoms such as O or N can supply short bonds and efficient overlap; oxo, imido and nitrido ligands are familiar examples. Early transition metals in high oxidation states, often $d^0$, are particularly favourable because the metal acceptor orbitals are vacant and relatively low in energy. More spatially extended $4d$ and $5d$ orbitals can strengthen the overlap.

Metal-to-ligand pi backbonding is the complementary case: electron-rich, low-oxidation-state metals donate occupied d orbitals into low-lying ligand antibonding orbitals, as for CO. In both directions, filling a metal–ligand pi-antibonding orbital offsets the multiple-bond stabilization. The relevant prediction is orbital occupancy and overlap, rather than the presence of a formal double-bond line in a drawing.

The active set contains four oxygen pi orbitals and two carbon pi orbitals, with eight electrons in six orbitals. The noninteracting levels, using the parameters inferred below, areEach bonding oxygen orbital has equal-phase coefficients on its two O atoms; its antibonding partner reverses one coefficient. The two pi directions are z in the prospective ring plane and y perpendicular to it. carbon pi and pi-star use z-directed p orbitals with equal and opposite coefficient signs. In this separated-fragment comparison the occupations are those of neutral triplet O${}_2$ plus neutral ethene. Do not refill the combined list solely by energy, which would move an electron between infinitely separated fragments and describe a charge-transfer state instead.

A $180^{\circ }$ rotation leaves both metal centres fixed but reverses each transverse p orbital: $p_x\mapsto -p_x$ and $p_y\mapsto -p_y$. Its matrix is $-I_4$, so its character of a representation is $\chi (C_6^3)=-4$, also obtained from $4\cos \pi$.

Choose transverse directions parallel and perpendicular to the vertical mirror plane. At each metal the parallel p orbital is unchanged, whereas the perpendicular p orbital changes sign. Thus each two-dimensional block has trace $1-1=0$. The total character of a representation is $\chi ({\sigma }_d)=0$. A mirror plane passing through an orbital centre does not imply that every orbital on that centre contributes $+1$.

This is an acid-catalysed alpha-ketol rearrangement. Label the original ketone carbon $C_A$ and the adjacent tertiary alcohol carbon $C_B$. Protonate the oxygen on $C_A$ to activate that carbonyl. The appropriately aligned cage C–C sigma bond attached to $C_B$ migrates onto $C_A$, while the hydroxyl oxygen at $C_B$ supplies its lone pair to form the new $C_B=O$ bond. At the same time the old $C_A=O$ pi bond moves onto oxygen, which becomes the new $C_A$–OH. deprotonation regenerates the acid.

The migration reroutes the bridge rather than removing water: the original alcohol carbon becomes the ketone, and the original ketone carbon becomes the tertiary alcohol. A productive conformation aligns the migrating sigma orbital with the accepting carbonyl pi-star orbital; the oxygen lone pair simultaneously overlaps the developing p orbital at the donor carbon. The cage's geometry controls which adjacent sigma bond has the necessary alignment and which less strained skeletal isomer results. A freely rotating isolated carbocation or a simple proton shift cannot account for the changed cage connectivity.

An electron occupying a pi-type molecular orbital. In a conjugated planar molecule, the pi subspace is commonly built from p orbitals perpendicular to the molecular plane; its electron population excludes the sigma framework.

Opposite parity of same-centre s orbitals and axial p orbitals makes their left and right nearest-neighbour hopping integrals opposite in sign. Their Bloch wave sum is consequently odd in wavevector and vanishes at the zone centre and boundary. Away from those points, orbital hybridization repels coupled levels and can produce an avoided crossing.