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A symmetry orbital is a linear combination of atomic orbitals transforming as a component of an irreducible representation of the molecular point group. A molecular orbital is a one-electron wavefunction for the molecule, obtained as an eigenfunction of the chosen effective one-electron Hamiltonian operator. Symmetry organizes the eigenproblem, but a symmetry label alone does not determine its coefficients.

Use the stipulated common Hückel Coulomb parameter $\alpha$, an equal Hückel resonance integral $\beta$ along each cube edge, and zero coupling elsewhere; take an orthonormal site basis. Each lithium vertex has three sodium neighbors. The totally symmetric combinations therefore have the blockFor a coordinate-like $T_2$ combination, the sum of the three neighboring sodium coordinate signs equals the lithium coordinate sign. Thus each of the three equivalent blocks isTheir eigenvalues give the cube nearest-neighbour Hückel model:For the bonding convention $\beta <0$ these are in increasing energy order, with statistical weights $1,3,3,1$. The eight valence electrons occupy $(a_1{)}^2(t_2{)}^6$, filling the four bonding spatial molecular orbitals. Their total one-electron energy is $8\alpha +12\beta$. This is a deliberately simplified model: unequal atomic energies or unequal overlaps require a generalized calculation.

At ${\beta }_L=0$, the preceding matrix separates into identical $({\varphi }_1,{\varphi }_2)$ and $({\varphi }_3,{\varphi }_4)$ blocks. For ${\beta }_S<0$, a normalized pair at the lower energy $\alpha +{\beta }_S$ isA pair at the upper energy $\alpha -{\beta }_S$ isThe four coefficient vectors are mutually orthonormal. Any orthogonal mixing within either equal-energy pair is an equally valid choice of molecular orbitals. At this limiting parameter value, additional coincidences with the one-dimensional levels occur: the full eight-orbital system is four isolated dimers, with four bonding and four antibonding levels.

Fill four spatial molecular orbitals with the eight $\pi$ electrons. For negative ${\beta }_S,{\beta }_L$ and $|{\beta }_S|>|{\beta }_L|$, the occupied energies are $\alpha +{\beta }_S+{\beta }_L$, $\alpha +{\beta }_S-{\beta }_L$, and the pair at $\alpha -\sqrt{{\beta }_S^2+{\beta }_L^2}$. ThereforeFor equal integrals, ${\beta }_S={\beta }_L=\beta <0$, this becomesAt equal bond lengths, the last two electrons occupy the frontier degeneracy at $E=\alpha$, so their distribution within that degenerate space does not change the bare Hückel method energy.

Each cyanide contributes charge $-1$, so the formal nickel oxidation state is $+2$ and the metal has $d^8$. The requested diagram retains only the five principally metal-$3d$ molecular orbitals; the mainly ligand bonding molecular orbitals lie below them and are omitted.

In the square, $d_{x^2-y^2}$ points directly towards all four ligand donors and gives the highest, strongly antibonding molecular orbital, $B_{1g}$. The $d_{z^2}$ function also has an allowed $A_{1g}$ interaction, but its in-plane overlap is smaller. Including the allowed nickel $4s$ mixing gives a principally $d$ $A_{1g}$ level with relatively weak antibonding character. The $B_{2g}$ and $E_g$ metal functions have no ligand partner in the sigma bond donor basis and are nonbonding in this minimal model. The useful qualitative ordering is thereforeThe three nonbonding functions are shown together because the sigma-only model does not determine their finer splitting. Additional electrostatic and pi backbonding interactions can change the ordering of the lower $d$ levels; molecular symmetry alone does not fix these energy gaps.^[ref]

In the tetrahedron, the ligand $T_2$ combinations interact with the metal $T_2$ functions, producing higher $d$-derived antibonding molecular orbitals. The metal $E$ pair has no sigma donor partner and remains nonbonding:The diagram fills both arrangements with eight metal electrons; the square is shown in its fully paired state.

For $n$ unpaired electrons, the spin-only magnetic moment iswhere ${\mu }_{\mathrm{B}}$ is the Bohr magneton and the second expression uses $g\simeq 2$.

For the square, a large separation of the highest $B_{1g}$ level favours pairing in the lower four molecular orbitals: $S=0$, $n=0$, ${\mu }_{\mathrm{eff}}=0$. If the cost of occupying $B_{1g}$ were smaller than the relevant electron pairing energy, a high-spin complex with two unpaired electrons and $S=1$ could instead occur, giving $\sqrt{8}{\mu }_{\mathrm{B}}\simeq 2.83{\mu }_{\mathrm{B}}$.

For ideal tetrahedral $d^8$, the occupation is $e^4{t}_2^4$. Hund's rules distribute four electrons over the three degenerate $t_2$ molecular orbitals as one pair and two single occupations. Thus $S=1$ and ${\mu }_{\mathrm{eff}}\simeq 2.83{\mu }_{\mathrm{B}}$. Merely increasing the $e$–$t_2$ splitting does not create a conventional paired tetrahedral $d^8$ alternative: four electrons must still occupy $t_2$.

Filling the three bonding molecular orbitals with two electrons each givesThree isolated ethene-like $\pi$ bonds, evaluated with the same Hückel method parameters, have $E_{\mathrm{loc}}=3\{2(\alpha +\beta )\}=6\alpha +6\beta$. Thus the signed delocalization energy isEquivalently, the positive stabilization is $-2\beta =2|\beta |$.

Benzene has a planar cyclic conjugated system with six $\pi$ electrons, satisfying the $4n+2$ count with $n=1$. All three bonding $\pi$ molecular orbitals are filled and the antibonding levels are empty, giving the closed-shell stabilization associated with aromaticity. The conclusion uses the continuous cyclic overlap as well as the electron count.

Use the printed numbering: site 1 is at the top on $+y$, sites 2 and 3 are on the right, site 4 is at the bottom, and sites 5 and 6 are on the left; $z$ is perpendicular to the ring. Let ${\chi }_j$ be consistently phased, orthonormal $p_z$ atomic orbitals at those sites.

In the Hückel method, $H_{jj}=\alpha$ and $H_{j,j\pm 1}=\beta$, including the 6–1 bond. Set $\lambda =(\epsilon -\alpha )/\beta$, with the usual $\beta <0$. The cyclic nearest-neighbour matrix has eigenvalues ${\lambda }_k=2\cos (2\pi k/6)$. One real, normalized orthonormal eigenbasis isEach row means $\psi ={\sum }_j{c}_j{\chi }_j$. The three lowest molecular orbitals hold the six $\pi$ electrons. Any real orthogonal mixing within either degenerate pair is an equally valid choice of molecular orbitals; the coefficient vectors specify exactly which sketches are used here.

The coloured circles show the signs and relative magnitudes of the lobes above the molecular plane. The lobes below it have the opposite signs; colours are quantum phases, not electric charges.

Work with $M=(H-\alpha I)/\beta$. Its nearest-neighbour ring entries are $1$, and its diagonal entries are $1$ on the nitrogen sites and $0$ on the carbon sites. Because $M$ commutes with each molecular symmetry operation, it only mixes symmetry-adapted linear combinations with the same irreducible representation.

In the bases $(N_{+},C_0)$ and $(N_{-},C_y)$, the two nontrivial matrix blocks areTheir characteristic polynomials are $(1-\lambda {)}^2-2$ and ${\lambda }^2-3$. The remaining single-function blocks are $M_{B_{2g}}=1$ and $M_{A_u}=-1$. Thus, ordered from lowest to highest physical energy because $\beta <0$, the molecular orbitals areAll six levels are nondegenerate in this parametrization. The right-hand ladder of the diagram in part (ii) shows these levels and occupations. The occupied $B_{2g}$ level is the highest occupied molecular orbital, and the unoccupied $B_{1u}$ level immediately above it is the lowest unoccupied molecular orbital.

The six $\pi$ electrons give the Hückel method energyThe appropriate localized reference contains two C=N $\pi$ bonds and one C=C $\pi$ bond. Three C=C bonds would incorrectly replace the nitrogen one-centre parameters. For one isolated C=N pair, the dimensionless matrix iswhose eigenvalues are $(1\pm \sqrt{5})/2$. Since $\beta <0$, the occupied bonding molecular orbital has energy $\alpha +(1+\sqrt{5})\beta /2$. Two doubly occupied C=N bonds and one doubly occupied C=C bond consequently giveTherefore the signed delocalization energy isThe positive stabilization is $1.82039|\beta |$, smaller than the benzene value $2|\beta |$ in the stated model but still stabilizing.

Pyrazine is aromatic: its planar cyclic conjugated system contains six $\pi$ electrons and has a filled set of three bonding $\pi$ molecular orbitals. Each ring nitrogen contributes one $p_z$ electron; its in-plane lone pair is outside this $\pi$ system. The heteroatoms change orbital energies and coefficients without interrupting cyclic conjugation or the $4n+2$ count. Aromaticity does not require the stabilization to equal benzene's.

The highest expected orbital degeneracy is five. Ideal buckminsterfullerene has Ih molecular point group symmetry. Its irreducible orbital representations include five-dimensional $H_g$ and $H_u$ representations; no single-valued orbital irrep has higher dimension.

This counts distinct spatial molecular orbitals. It does not multiply by electron spin, and it excludes accidental coincidences between unrelated irreps. In a real environment, symmetry lowering can split these degeneracies.^[ref]

Set $E=\alpha +\lambda \beta$, with the usual bonding convention $\beta <0$. In the Hückel method, the dimensionless matrix $M=(H-\alpha I)/\beta$ has diagonal entries one on oxygen sites 1 and 8, zero on carbon, and unit entries between bonded neighbours. In the bases $(O_{+},C_{+},R_{+})$ and $(O_{-},C_{-},R_{-})$ above, its blocks areThe one-dimensional $B_{2g}$ and $A_u$ blocks have $\lambda =1$ and $-1$, respectively. The characteristic polynomial of the $B_{1u}$ block factors asso its three molecular orbital energies areFor the $B_{3g}$ block the matrix trace is zero. Thus its three $\lambda$ values sum to zero, and the pair supplied in the paper gives the remaining one as $-(1.86-2.12)\simeq 0.26$. Directly, its secular equation is ${\lambda }^3-4\lambda +1=0$, whose roots are approximately $1.860806$, $0.254102$ and $-2.114908$. The supplied pair is approximate, so $0.26$ from its trace and $0.2541$ from the exact block should not be mistaken for an additional physical splitting.

All eight energies, ordered from low to high for $\beta <0$, areThe eight $\pi$ electrons fill the four lowest molecular orbitals. The equality at $\lambda =1$ is an accidental degeneracy of this parameterized model, not a multidimensional representation of $D_{2h}$.

The chloride complex has Pt(II), $d^8$, whereas the neutral bis(phosphine) complex has Pt(0), $d^{10}$ in the neutral-ethene assignment. The lower-valent, phosphine-supported Pt(0) centre back-donates more strongly into ethene ${\pi }^{\ast }$, weakening and lengthening its internal C–C bond. This accounts for the longer $1.430\text{A˚}$ distance compared with $1.375\text{A˚}$ in the Pt(II) complex.

Both are formally 16-electron complexes: $8+3(2)+2=16$ for the chloride species and $10+2(2)+2=16$ for the phosphine species. Thus the difference is not simply a difference in total valence count. It reflects the energies and occupations of the metal–ligand molecular orbitals. The increased reduction of the ethene ligand gives the Pt(0) complex more metallacyclopropane character; the two descriptions are bonding limits, not distinct products inferred from the distances alone.

The carbon end of a carbonyl ligand has a filled $5\sigma$ molecular orbital with an outward-facing lobe. Its overlap with a vacant metal orbital of the same axial symmetry gives CO-to-metal sigma donation. Occupied metal $d_{\pi }$ orbitals can simultaneously overlap with the empty CO $2{\pi }^{\ast }$ antibonding molecular orbitals, giving metal-to-CO pi backbonding. Two perpendicular pi channels are possible; the schematic represents one. Orbital signs indicate phase, not electric charge.

The two interactions reinforce one another: sigma donation transfers density toward the metal, and pi backbonding distributes it into the ligand acceptor orbitals. Both strengthen M–C attachment, while backbonding weakens C–O. Occupation of CO ${\pi }^{\ast }$ decreases the internal C–O bond order, generally increasing its bond length and lowering its stretching spectroscopic wavenumber. This is why a strongly backbonded carbonyl ligand can have a strong metal–carbon bond and a weakened internal carbon–oxygen bond at the same time.

The dimer has two unpaired electrons and a triplet ground state, $S=1$. Its approximately threefold-symmetric Fe${}_2$(CO)${}_3$ core supplies a pair of degenerate frontier molecular orbitals. The last two electrons occupy separate members with parallel spins, favored by exchange, rather than pairing in one. A useful qualitative picture is a sigma bond plus two perpendicular, singly occupied pi half-bonds: together these support a formal Fe–Fe double bond while retaining paramagnetism. The spin-only magnetic moment for $S=1$ is $\sqrt{8}{\mu }_B\simeq 2.83{\mu }_B$; real moments can include orbital and spin–orbit effects.

The formal 18-electron count does not require every molecular orbital to be doubly occupied. It is therefore compatible with an open-shell dimer. The primary structural/magnetic study establishes this unusual triplet state; an isolated-atom high-spin $d^7$ diagram would not describe the coupled metal–ligand system.^[ref]

The filled alkene $\pi$ molecular orbital donates into a vacant metal acceptor orbital directed toward the center of the C=C bond. In the reverse direction, a filled metal $d$ orbital can overlap with the alkene ${\pi }^{\ast }$ antibonding molecular orbital. These are the donation and pi backbonding components of the Dewar-Chatt-Duncanson model, illustrated in the lower part of the bonding schematic. The alkene is an ${\eta }^2$ alkene ligand, attached through both carbons. Increasing backbonding weakens and lengthens C=C and can push the bonding toward a metallacyclopropane description.

Zr(IV) is $d^0$, so alkene-to-metal donation predominates. It has suitable empty orbitals but no occupied metal $d$ set to provide substantial conventional backbonding. An electron-deficient cationic zirconocene can consequently bind and activate an alkene largely through its Lewis acidity; it should not be drawn as a strongly backbonded late-metal alkene merely because its formal coordination mode is ${\eta }^2$.

The nitrite ion is an ambidentate ligand: its Lewis structures leave donor lone pairs on both nitrogen and oxygen. In the N-bound mode, $\mathrm{M}-\mathrm{N}(\mathrm{O}{)}_2$, the nitrogen lone pair makes a sigma bond to the metal, while a suitable unoccupied nitrite molecular orbital can accept metal $d$ electron density by pi backbonding. Thus N-bound nitro is a sigma donor and pi acceptor. The nitrite group remains bent at nitrogen; N coordination does not make it a linear nitrosyl.

In the O-bound mode, $\mathrm{M}-\mathrm{O}-\mathrm{N}=\mathrm{O}$, an oxygen lone pair makes the metal–oxygen sigma bond. A second occupied oxygen orbital can donate sideways into an available metal orbital: O-bound nitrito is a sigma and pi donor, rather than the strong pi acceptor of the N-bound description. oxygen's greater electronegativity lowers its donor orbital energies, but the occupied oxygen orbitals still explain its pi-donor classification. Actual mixing depends on metal oxidation state and geometry.

A further possibility is bidentate coordination, $\mathrm{M}({\kappa }^2\text{-}O,O\text{-}\mathrm{N}{\mathrm{O}}_2)$, with both oxygen atoms attached to one metal. Each attachment has oxygen-to-metal sigma donation; additional pi donation depends on orbital alignment. nitrite can also be a bridging ligand between metals. Neither alternative should be confused with linkage isomerism, which specifically compares attachment through different atoms at the same binding site.

A carbonyl ligand binds through carbon, whose occupied $5\sigma$ molecular orbital has a substantial outward-facing carbon lobe. Overlap with an empty metal orbital along the M–C axis gives ligand-to-metal sigma donation. Conversely, an occupied metal $d_{\pi }$ orbital overlaps sideways with an empty CO $2{\pi }^{\ast }$ antibonding molecular orbital, giving metal-to-ligand pi backbonding. There are two mutually perpendicular pi channels. The original orbital schematic below shows one of them; $+$ and $-$ denote orbital phase, not electric charge.

The interactions are synergic: donation makes electron density available at the metal, and backbonding helps accommodate it while strengthening the metal–carbon interaction. Occupying CO ${\pi }^{\ast }$ reduces the C–O bond order, lengthens that bond and lowers its bond force constant. Therefore stronger pi backbonding generally lowers the carbonyl stretching spectroscopic wavenumber even while strengthening the M–C attachment.

Take the bond axis as $z$. The heavy-atom $2s$ and $2p_z$ atomic orbitals can mix with hydrogen $1s$ to make three sigma-symmetry molecular orbitals. In the qualitative valence ordering, these are a low predominantly heavy-atom $2s$ level, a bonding $\sigma$ level and a higher ${\sigma }^{\ast }$ level. The perpendicular $2p_x,2p_y$ orbitals form a degenerate approximately nonbonding $\pi$ pair because hydrogen has no valence orbitals of the matching sideways symmetry. The filled heavy-atom $1s$ core is omitted from the diagram.

Counting valence electrons givesThus both exhibit paramagnetism: CH has one unpaired electron and NH has two in its ground state. For NH, Hund's rules favour separate parallel-spin occupation of the two degenerate $\pi$ orbitals. The corresponding observed ground terms are $X{}^2\Pi$ and $X{}^3{\Sigma }^{-}$; the total bond order is approximately one in this simple sigma-bond/nonbonding-pi description.^[ref]

The nitrogen-derived orbital energies lie lower than the corresponding carbon-derived ones on an approximate common energy scale, while the isolated hydrogen $1s$ reference is unchanged. The bonding orbitals consequently have different polarizations and mixing coefficients; drawing identical energies for C and N would miss the screening trend. The figure specifies ordering and occupancy, not measured gaps or a numerical prediction from (a).

The elementary valence-MO model gives $\boxed{\text{bond order}({\mathrm{C}}_2)=2}$. Each carbon supplies four $n=2$ valence electrons, so fill eight electrons in the ordering appropriate to the lighter second-row diatomics:The two ${\pi }_u$ orbitals are degenerate, as are the two ${\pi }_g^{\ast }$ orbitals. The $2s$ bonding and antibonding occupations cancel; four net p-bonding electrons remain, giving $(6-2)/2=2$. Mixing between sigma orbitals of compatible symmetry places the occupied ${\pi }_u$ pair below the empty p-derived ${\sigma }_g$ orbital in this diagram. All occupied orbitals are paired.

The omitted $1s$ orbitals form filled ${\sigma }_{g}1s$ and ${\sigma }_u^{\ast }1s$ levels. Their contributions to the formal bond order cancel, and their low energies and small spatial extent make them largely core-like. Omitting them simplifies this valence diagram without claiming they do not exist or have exactly no effect on molecular energies.