Valence Bond theory, as we saw in the last section,
is based on the notion that electrons are localized to specific atomic orbitals. Molecular orbital theory asserts that atomic orbitals no longer hold significant meaning after atoms form molecules. Electrons no longer "belong", in a sense, to any particular atom but to the molecule as a whole. Molecular orbital theory holds, as its name suggests, that electrons reside in molecular orbitals that are distributed over the entire molecule.
Quantum mechanics specifies that we can get molecular orbitals through a linear combination of atomic orbitals; that is, by adding and subtracting them. How do we add and subtract orbitals? The best way to picture this process is to recall the wave-like nature of electrons. Recall from physics that two waves can interact either through constructive interference, in which the two waves reinforce each other, and destructive interference, in which the two waves cancel each other out. Mathematically, constructive interference corresponds to addition and destructive interference corresponds to subtraction. When atomic orbitals interact, we can either add them to obtain a bonding orbital or subtract them to obtain an antibonding orbital. Antibonding orbitals are denoted with an asterisk (*).
For instance, in the hydrogen molecule, the atomic 1 s orbitals can overlap in a (head-on) fashion to form a -bonding molecular orbital and a - antibonding molecular orbital. The bonding molecular orbital is "bonding" in the sense that it is lower in energy than its component atomic orbitals. Forming a bond and moving electrons into the bonding orbital lowers the total energy of the system, which is favorable. On the other hand, moving electrons into the antibonding orbital raises the energy of the system, which disfavors bond formation. The total number of orbitals is conserved; the number of molecular orbitals equals the number of original atomic orbitals.
Polar Bonds When the bonding atoms significantly differ in electronegativity, their orbital energies will also be different. Compare the MO picture of hydrogen with that of H-F. Because fluorine is more electronegative than hydrogen, its 2p orbitals lie below the 1s orbitals of hydrogen. Due to this difference in energy, the stabilization energy of the resulting bonding MO is not as large. Furthermore, the bonding MO is much more like the 2p orbital in its spatial characteristics while the antibonding MO is much more like the 1s orbital. Energy Considerations One advantage of the MO Model is that it gives us more information about the energies of the bonding electrons. In the case of H 2 , the molecule is stabilized by twice the E of the bonding orbital. The larger this energy gap, the more stable the bond. In order for this stabilization energy to be large, several factors are important:
The atoms must be of similar electronegativity. Atoms must be of comparable size. Orbitals must achieve adequate spatial overlap. For example, the fact that the O-H bond is stronger than the S-H bond can be explained by item 2. The 2p orbital of oxygen can overlap with the 1s orbital of hydrogen more effectively than it can with the 3p orbital of sulfur. Finally, item 3 correctly predicts that bonds should be stronger than bonds since they have a greater degree of direct overlap.
Bond Order How does MO theory describe multiple bonds? In MO theory the bond order of a bond is the number of bonding electron pairs minus the number of antibonding electron pairs. Intuitively, bonding electrons stabilize the bond while antibonding electron destabilize the bond. The greater this difference, the stronger the bond, and the higher the bond order. As we'll see, in MO theory the bond order is no longer limited to integer values.
Electron Delocalization One of the greatest successes of MO theory is that it accounts for electron delocalization in a natural way. We have seen that some molecules require resonance structures to be represented accurately. In all such cases, electrons are delocalized over several bonds/atoms. One main drawback of the VB model is that it assigns electrons to specific atoms/bonds and therefore breaks down when it comes to explaining delocalized electrons. The MO model has no such problem; it offers a clean approach to describing delocalization that is superior to writing a bunch of awkward resonance structures. Application of MO Theory to Extended -systems Unfortunately, the complexity of the full MO model increases exponentially with the size of the molecule. In order for MO theory to be useful in practice, we limit its application to portions of a molecule that are extensively delocalized. This often occurs when electrons and lone pairs overlap over several contiguous atoms. MOLECULAR ORBITAL THEORY 1. Molecular orbitals (MOs) are made of fractions of atomic orbitals. All atoms in the molecule provide their atomic orbitals for construction of MOs, but not all atomic orbitals must participate in all MOs. The number of MOs is equal to the number of atomic orbitals used to generate them. Instead of making bonds one at a time by overlapping pairs of atomic or hybridized orbitals, in the the MO procedure all available atomic orbitals are mixed into multiple combinations (MOs). This mixing procedure is called the Linear Combination of Atomic Orbitals (LCAO), and it simply means that we "add" and "subtract" fractions of atomic orbitals (wavefunctions) to make new molcular orbitals. We have to use each atomic orbital completely, we have to generate normalized molecular orbitals (MOs), and the number of MOs must be equal to the number of atomic orbitals that we have started with. Again, it is a bit like making mixed drinks (except for the "subtracting" part), but now we mix orbitals of different atoms all at once, instead of just premixing individual atom's orbital as we din inhybridization. 2. The MO are delocalized over many atoms. In general, they do not directly correspond to specific bonds (the exceptions include simple diatomic molecules or some isolated bonds, such as one in ethylene).
Since many atomic orbitals participate in the "mixture" to form the molecular orbitals, the volumes of these new orbitals encompass many atoms, sometimes even the whole molecule. The so formed MOs do not any longer correspond to specific bonds (as they were in VB theory). In fact, they can be bonding between some pairs of atoms (where "addition" of wavefunctions took place) and antibonding between other pairs of atoms (where "subtraction" of wavefunctions happend), and sometimes they will have a node at a given atom (like in the allyl system). On some occasions the MO and VB orbitals will "look" exactly the same. For example, we may find such cases in isolated bonds, or orbitals containing lone pairs that are not adjacent to systems. 3. The (or *) type MOs are usually separated from (or *) type MOs. (One exception that will be discussed by us is called hyperconjugation). This separation is the consequence of symmetry. bonds are usually perpendicular to bonds, i.e. they cannot mix (because the overlap is zero). In many cases this arrangement simply means that and networks do not interact and can be treated separately. This situation simplifies the analysis. For example, look at benzene: its and networks are essentially independent; when we analyze benzene (and aromaticity later on) we talk exclusively about electrons. Of course, there are exceptions. There are many situations where bonds are in geometry that allows for overlap with a system. One such exception is called hyperconjugation. In fact, the concept is (again) derived from the VB theory to account for the delocalization of electrons from the bond to the system. And likeresonance (= conjugation) it is a fix of our model, and not the problem of molecular structure. In MO theory, the hyperconjugation shows naturally: the appropriate, mostly - type MO show contributions from some atomic orbitals (s or p) of adjacent atoms that are properly aligned with the system (but would not be, in the VB language, considered a part of it). 4. The MO are filled by all available electrons (no more than two per orbital), starting from the lowest energy MO orbital. Each MO has energy associated with it (see above). All available electrons (from all participating atoms) are placed (two per orbital) in the molecular orbitals, starting at the bottom of the energy scale and moving up, until no more electrons are left. What counts is not whether the orbital is bonding or antibonding between specific atoms within the molecule, but what is the energy of the orbital. 5. All electrons in all MOs determine the structure of the molecule, but the Highest (in energy) Occupied MO (HOMO) and the Lowest (in energy) Unoccupied MO (LUMO) are the most important from the point of view of reactivity. The energy of the specific molecular structure depends on energy of its electrons in occupied molecular orbitals. Different structures (i.e. molecular geometries) will have different energies of their molecular orbitals. Thus, all electrons will influence the structure (remember the compromises discussed above). But from the point of view of reactivity some electrons and some orbitals are more important than others. The electrons of the highest energy are the ones that the molecule would like to "dump", and empty orbitals of the lowest energy (in the reaction partner) are the best "dumping grounds". In some chemical reactions (for example electron-transfer reactions or Lewis acid-base coplex formations) this is exactly what takes place, in others the interactions between the HOMO (occupied) and the LUMO (unoccupied) "starts" the reorganization of bonding of both reacting partners. 6. The usual energy ordering of MOs is as follows: -type orbitals (the lowest energy), - type orbitals, nonbonding orbitals (atomic orbitals, lone pair orbitals, or non-bonding - type orbitals), *-type orbitals and *-type orbitals (the highest in energy). The exceptions are known (for example, CO molecule). This ordering may be used to rapidly identify the HOMO and the LUMO in organic molecules 7. In general for each type ( or ) the energy of the MO increases with the increasing number of nodes (in the bonding sense). Predicting the ordering of the energy levels of the orbitals that are farther removed from the line dividing the occupied and unoccupied orbitals is more difficult, short of performing calculations. But we rarely need it anyway. On the other hand, it is useful to know that the energy of each type of orbital ( and especially ) increases with the number of nodes. Here, we want to count the nodes that result in antibonding interaction between atoms that are bonded in the molecule. The more nodes of this type, the higher the energy of the orbital. So, although we cannot order the and type orbitals relative to each other, we can arrange the orbitals according to their energy and decide easily (for example) which is the highest occupied. 8. The electronegativity of atoms is reflected in the size of their lobes within the MO. Usually, in bonding orbitals there is more participation (the lobes are larger) by the more electronegative atoms. In the corresponding antibonding orbitals the lobe sizes are reversed. The situation here is slightly complicated. The size of the lobe of the atomic orbital participating in a given molecular orbital depends on the energy of that orbital and its size (these two are of course related, see above). The bonding molecular orbital will have larger contributions from the lower energy (i.e. more electronegative) atoms, and the antibonding orbitals will have larger contributions from the higher energy (i.e. less electronegative) atoms. This usually works well for atoms from the same row of periodic table, but deviations from this pattern can be expected if the orbital lobes are contributed by atoms belonging to different rows (compare for example the size of the p orbitals of oxygen and sulfur in the table in Part I). 9. Most often, the HOMO corresponds to a filled -type orbital or a lone pair (nonbonding electrons), and the LUMO corresponds to an empty atomic p, *-type orbital or (if there is no system) to an empty * orbital. This is just the consequence of orbital ordering discussed in p. 6. A minor complication (not really) is when a lone pair orbital is part of the system (as happens when resonance is present). Well... then the whole system: needs to be analyzed. Typically, the HOMO in such situations is an occupied nonbonding type orbital. 10. The chemical reactions between molecules are largely governed by HOMO-LUMO interactions (the highest-energy electrons (HOMO) of one molecule "looking for" the lowest-energy unfilled space (LUMO) in the other molecule). The electron-rich component's (see: Brnsted base, Lewis base, nucleophile, electron donor) HOMO will interact strongly with the electron-deficient component's (see: Brnsted acid, Lewis acid, electrophile, electron acceptor) LUMO. The difference in energy between these orbitals and the overlap between them (orbital lobe size) will largely determine the facility of the reaction and the site of attack (bond formation).
Since interaction between filled (occupied) orbitals does not result in net bonding (electron- electron repulsion), and interaction between empty (unoccupied) orbitals cannot contribute to bonding (no electrons to be shared) only the interaction between occupied and unoccupied orbitals may provide the initial impetus for the reorganization of existing bonding. Of course the highest energy electrons (HOMO) and the lowest energy empty orbitals (LUMO) will interact the strongest (they are closest in energy, see above). Essentially all chemical reactions are dependent on these HOMO-LUMO interactions. The strength of interaction between orbitals is proportional to their overlap (here assumed the same for both pairs of interaction) and inversely proportional to their energy separation. HOMOB LUMOA interaction will control the reactivity between A (Lewis acid or electrophile) and B (Lewis base or nucleophile).